KR20120120906A - Novel organic dye and preparation thereof - Google Patents
Novel organic dye and preparation thereof Download PDFInfo
- Publication number
- KR20120120906A KR20120120906A KR1020120042542A KR20120042542A KR20120120906A KR 20120120906 A KR20120120906 A KR 20120120906A KR 1020120042542 A KR1020120042542 A KR 1020120042542A KR 20120042542 A KR20120042542 A KR 20120042542A KR 20120120906 A KR20120120906 A KR 20120120906A
- Authority
- KR
- South Korea
- Prior art keywords
- compound
- formula
- dye
- chemical formula
- mmol
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 170
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000000126 substance Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims abstract description 9
- 239000010419 fine particle Substances 0.000 claims abstract description 7
- 125000006850 spacer group Chemical group 0.000 claims abstract description 6
- -1 cyano, hydroxyl Chemical group 0.000 claims description 60
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000001072 heteroaryl group Chemical group 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 13
- 125000002252 acyl group Chemical group 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 12
- 150000001345 alkine derivatives Chemical class 0.000 claims description 12
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 150000001925 cycloalkenes Chemical class 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical group OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 3
- 125000005843 halogen group Chemical group 0.000 claims 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 48
- 239000000975 dye Substances 0.000 description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000012044 organic layer Substances 0.000 description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- 239000000370 acceptor Substances 0.000 description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 238000006619 Stille reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 3
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940126086 compound 21 Drugs 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- HUCFDUOIMSRYAA-UHFFFAOYSA-N 1-bromo-4-(2,2-diphenylethenyl)benzene Chemical compound C1=CC(Br)=CC=C1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 HUCFDUOIMSRYAA-UHFFFAOYSA-N 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 1
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 description 1
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 1
- AHUQRGHAKJSUKU-UHFFFAOYSA-N 1,4-bis[5-(1-benzofuran-2-yl)thiophen-2-yl]-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-3,6-dione Chemical compound C1=CC=C2OC(C3=CC=C(S3)C3=C4C(=O)N(C(=C4C(=O)N3CC(CC)CCCC)C=3SC(=CC=3)C=3OC4=CC=CC=C4C=3)CC(CC)CCCC)=CC2=C1 AHUQRGHAKJSUKU-UHFFFAOYSA-N 0.000 description 1
- YIUHGBNJJRTMIE-UHFFFAOYSA-N 1,4-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-3,6-dione Chemical compound C=12C(=O)NC(C=3SC=CC=3)=C2C(=O)NC=1C1=CC=CS1 YIUHGBNJJRTMIE-UHFFFAOYSA-N 0.000 description 1
- YLRBJYMANQKEAW-UHFFFAOYSA-N 1-bromo-4-(bromomethyl)benzene Chemical compound BrCC1=CC=C(Br)C=C1 YLRBJYMANQKEAW-UHFFFAOYSA-N 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- GPWNWKWQOLEVEQ-UHFFFAOYSA-N 2,4-diaminopyrimidine-5-carbaldehyde Chemical compound NC1=NC=C(C=O)C(N)=N1 GPWNWKWQOLEVEQ-UHFFFAOYSA-N 0.000 description 1
- YWRQUVDGOPUXJP-UHFFFAOYSA-N 2,5-dioctyl-1,4-dithiophen-2-ylpyrrolo[3,4-c]pyrrole-3,6-dione Chemical class CCCCCCCCN1C(=O)C2=C(C=3SC=CC=3)N(CCCCCCCC)C(=O)C2=C1C1=CC=CS1 YWRQUVDGOPUXJP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XLBJRZQXKFBBPL-UHFFFAOYSA-N 2-hexylthieno[2,3-c]thiophene Chemical compound S1C=C2SC(CCCCCC)=CC2=C1 XLBJRZQXKFBBPL-UHFFFAOYSA-N 0.000 description 1
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 1
- UJYNKHZRWUXZNV-UHFFFAOYSA-N 2H-thieno[3,2-b]thiophen-5-one Chemical compound O=C1SC2=CCSC2=C1 UJYNKHZRWUXZNV-UHFFFAOYSA-N 0.000 description 1
- JXSVIVRDWWRQRT-SVOQGVCWSA-N 2alpha,3alpha,23-trihydroxyurs-12-en-28-oic acid Chemical compound C1[C@@H](O)[C@@H](O)[C@@](C)(CO)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C JXSVIVRDWWRQRT-SVOQGVCWSA-N 0.000 description 1
- VGKLVWTVCUDISO-UHFFFAOYSA-N 3,4-dibromothiophene Chemical compound BrC1=CSC=C1Br VGKLVWTVCUDISO-UHFFFAOYSA-N 0.000 description 1
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 description 1
- KTJVNIAXMXJVMI-UHFFFAOYSA-N 3-bromo-4-oct-1-ynylthiophene Chemical compound CCCCCCC#CC1=CSC=C1Br KTJVNIAXMXJVMI-UHFFFAOYSA-N 0.000 description 1
- UCFSYHMCKWNKAH-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OBOC1(C)C UCFSYHMCKWNKAH-UHFFFAOYSA-N 0.000 description 1
- MRWWWZLJWNIEEJ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-propan-2-yloxy-1,3,2-dioxaborolane Chemical compound CC(C)OB1OC(C)(C)C(C)(C)O1 MRWWWZLJWNIEEJ-UHFFFAOYSA-N 0.000 description 1
- LECGHFZOZHNNCP-UHFFFAOYSA-N 5-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=C(Br)SC=C21 LECGHFZOZHNNCP-UHFFFAOYSA-N 0.000 description 1
- ZHGCYMIPTCLQLH-UHFFFAOYSA-N C1=CC(C=[SiH]1)(c1ccccc1)c1ccccc1 Chemical compound C1=CC(C=[SiH]1)(c1ccccc1)c1ccccc1 ZHGCYMIPTCLQLH-UHFFFAOYSA-N 0.000 description 1
- KZQDKDRMSDVWEY-UHFFFAOYSA-N C1=CC=CC=C1[PH2](C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound C1=CC=CC=C1[PH2](C=1C=CC=CC=1)C1=CC=CC=C1 KZQDKDRMSDVWEY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920003944 DuPont™ Surlyn® 1702 Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 1
- RODWDXFRRQSGRP-UHFFFAOYSA-N [I+].C(CCCCC)N1C(=[N+](C=C1)C)C Chemical compound [I+].C(CCCCC)N1C(=[N+](C=C1)C)C RODWDXFRRQSGRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940125810 compound 20 Drugs 0.000 description 1
- 229940126208 compound 22 Drugs 0.000 description 1
- 229940125833 compound 23 Drugs 0.000 description 1
- 229940127204 compound 29 Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- YPLYFEUBZLLLIY-UHFFFAOYSA-N dipropan-2-yl butanedioate Chemical compound CC(C)OC(=O)CCC(=O)OC(C)C YPLYFEUBZLLLIY-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- UMIPWJGWASORKV-UHFFFAOYSA-N oct-1-yne Chemical compound CCCCCCC#C UMIPWJGWASORKV-UHFFFAOYSA-N 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical group O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CUPOOAWTRIURFT-UHFFFAOYSA-N thiophene-2-carbonitrile Chemical compound N#CC1=CC=CS1 CUPOOAWTRIURFT-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- SQRICDVGYLFTLO-UHFFFAOYSA-N tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)stannane Chemical compound O1CCOC2=C([Sn](CCCC)(CCCC)CCCC)SC=C21 SQRICDVGYLFTLO-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
- Y02E10/542—Dye sensitized solar 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
본 발명은 염료감응태양전지 (dye-sensitized solar cell, DSSC)에 사용되는 신규한 염료 및 이의 제조방법에 관한 것이다.
The present invention relates to a novel dye used in dye-sensitized solar cells (DSSC) and a method for producing the same.
1991년도 스위스 국립 로잔 고등기술원 (EPFL)의 마이클 그라첼 (Michael Gratzel) 연구팀에 의해 염료감응 나노입자 산화티타늄 태양전지가 개발된 이후 이 분야에 관한 많은 연구가 진행되고 있다. 염료감응태양전지는 기존의 실리콘계 태양전지에 비해 효율이 높고 제조단가가 현저히 낮기 때문에 기존의 비정질 실리콘 태양전지를 대체할 수 있는 가능성을 가지고 있으며, 실리콘 태양전지와 달리 염료감응태양전지는 가시광선을 흡수하여 전자-홀 (hole) 쌍을 생성할 수 있는 염료분자와, 생성된 전자를 전달하는 전이금속 산화물을 주 구성 재료로 하는 광전기 화학적 태양전지이다.Since the development of dye-sensitized nanoparticle titanium oxide solar cells by the team of Michael Gratzel of the Swiss National Lausanne Institute of Advanced Technology (EPFL) in 1991, much work has been done in this area. Dye-sensitized solar cells have the potential to replace conventional amorphous silicon solar cells because of their higher efficiency and lower manufacturing costs than conventional silicon-based solar cells. It is a photoelectrochemical solar cell whose main component is a dye molecule capable of absorbing and generating electron-hole pairs, and a transition metal oxide for transferring generated electrons.
염료감응태양전지에 사용되는 염료로서 높은 광전기 전환효율을 나타내는 루테늄 금속 착체가 널리 사용되어 왔는데, 이 루테늄 금속 착체는 가격이 너무 비싸다는 단점이 있었다.As a dye used in dye-sensitized solar cells, ruthenium metal complexes having high photovoltaic conversion efficiency have been widely used, but this ruthenium metal complex has a disadvantage of being too expensive.
최근, 흡광효율, 산화환원 반응 안정성 및 분자내 전하-전달 (charge-transfer, CT)계 흡수의 측면에서 우수한 물성을 나타내는, 금속을 함유하지 않은 유기염료가, 고가의 루테늄 금속 착체를 대체할 수 있는 태양전지용 염료로서 사용될 수 있음이 발견되어, 금속이 결여된 유기염료에 대한 연구가 중점적으로 이루어지고 있다.Recently, metal-free organic dyes, which exhibit excellent physical properties in terms of light absorption efficiency, redox reaction stability, and intramolecular charge-transfer (CT) -based absorption, can replace expensive ruthenium metal complexes. It has been found that it can be used as a dye for solar cells, and research on organic dyes lacking metals has been focused on.
유기염료는 일반적으로 π-결합 유닛에 의해 연결되는 전자 공여체 (electron donor)-전자 수용체 (electron acceptor) 잔기의 구조를 갖는다. 대부분의 유기염료에서, 아민 유도체가 전자 공여체의 역할을 하고, 2-시아노아크릴산 또는 로다닌 잔기가 전자 수용체의 역할을 하며, 이 두 부위는 메타인 유닛 또는 티오펜 체인과 같은 π-결합 시스템에 의해 연결된다.Organic dyes generally have a structure of electron donor-electron acceptor residues linked by π-binding units. In most organic dyes, amine derivatives act as electron donors, 2-cyanoacrylic acid or rhodanine residues act as electron acceptors, and these two sites are π-binding systems such as metaine units or thiophene chains. Is connected by.
일반적으로, 전자 공여체인 아민 유닛의 구조적 변화는 전자 특성의 변화, 예를 들어 청색 쪽으로 쉬프트 (shift)된 흡광 스펙트럼을 가져오고, π-결합 길이를 변화시켜 흡광 스펙트럼과 산화환원 전위 (redox potential)를 조절할 수 있다.In general, the structural change of the amine unit, which is an electron donor, results in a change in the electronic properties, for example, an absorption spectrum shifted towards blue, and by changing the π-bond length, the absorption spectrum and redox potential. Can be adjusted.
그러나 이제까지 알려진 대부분의 유기염료는 루테늄 금속 착체 염료에 비해 낮은 변환효율과 낮은 구동 안정성을 나타내므로, 이러한 전자 공여체와 수용체의 종류 또는 π-결합 길이를 변화시킴으로써, 기존의 유기염료 화합물들에 비해 향상된 몰흡광계수를 가지며 높은 광전기 변환효율을 나타내는 새로운 염료를 개발하려는 노력이 지속되고 있는 실정이다.However, most of the organic dyes known so far have lower conversion efficiency and lower driving stability than ruthenium metal complex dyes. Thus, by changing the type of electron donor and acceptor or the π-bond length, the organic dyes are improved compared to the conventional organic dye compounds. Efforts have been made to develop new dyes having a molar absorption coefficient and showing high photoelectric conversion efficiency.
따라서 본 발명은 종래의 염료보다 향상된 HOMO-LUMO 에너지 갭, 몰흡광계수 및 광전기 변환효율을 나타내어 태양전지의 효율을 크게 향상시킬 수 있는 유기염료 및 이의 제조방법을 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide an organic dye and a method of manufacturing the same, which can improve the efficiency of a solar cell by exhibiting an improved HOMO-LUMO energy gap, a molar absorption coefficient, and a photoelectric conversion efficiency than a conventional dye.
또한 본 발명은 상기 염료를 포함하여 현저히 향상된 HOMO-LUMO 에너지 갭 및 광전기 변환효율을 나타내며, Jsc (단회로 광전류 밀도, short circuit photocurrent density)와 몰흡광계수가 우수한 염료증감 광전변환소자, 및 효율이 현저히 향상된 태양전지를 제공하는 것을 목적으로 한다.
In addition, the present invention exhibits a markedly improved HOMO-LUMO energy gap and photoelectric conversion efficiency including the dye, a dye-sensitized photoelectric conversion device having excellent J sc (short circuit photocurrent density) and molar absorption coefficient, and efficiency It is an object to provide this remarkably improved solar cell.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 유기염료를 제공한다.In order to achieve the above object, the present invention provides an organic dye represented by the following formula (1).
[화학식 1][Formula 1]
DO - Qm - B - Qn - ACDO-Qm-B-Qn-AC
상기 화학식 1에서,In Formula 1,
B는 
Q는 
DO는 지방족 화합물을 포함하는 전자 주개 그룹으로서, 바람직하게는 C1-50의 알킬, 이소알킬(가지형 알킬), 아릴, 알콕시, 알켄, 알킨, 실록시, 아민, 할로겐, 시아노, 하이드록실, 니트로, 아실, 아릴 또는 헤테로아릴기로 치환되거나 치환되지 않은 C1-50의 알킬, 아릴, 알콕시 또는 헤테로아릴이며;DO is an electron donor group containing an aliphatic compound, preferably C 1-50 alkyl, isoalkyl (branched alkyl), aryl, alkoxy, alkene, alkyne, siloxy, amine, halogen, cyano, hydroxyl C 1-50 alkyl, aryl, alkoxy or heteroaryl, optionally substituted with nitro, acyl, aryl or heteroaryl groups;
AC는 시아노아크릴산기를 포함하는 전자 받개 그룹으로서, 바람직하게는 하나 이상의 할로겐, C1-10 알킬, 또는 모노, 디 또는 트리페닐메틸로 치환되거나 치환되지 않은 시아노아크릴산기이고;AC is an electron acceptor group comprising a cyanoacrylic acid group, preferably a cyanoacrylic acid group which is optionally substituted with one or more halogen, C 1-10 alkyl, or mono, di or triphenylmethyl;
R1, R2, R3, R4, Y 및 Z는 각각 독립적으로 수소, 또는 헤테로 원자 또는 치환기로 치환되거나 치환되지 않은 1 내지 50의 탄소 수를 가지는 알킬, 이소알킬 (가지형 알킬), 아릴, 알콕시, 헤테로아릴, 알켄, 알킨, 실록시, 시아노, 하이드록실, 니트로, 아민, 아실, 시클로알켄 또는 시클로알킨이고;R 1 , R 2 , R 3 , R 4 , Y and Z are each independently hydrogen or alkyl having 1 to 50 carbon atoms, unsubstituted or substituted with a hetero atom or a substituent, isoalkyl (branched alkyl), Aryl, alkoxy, heteroaryl, alkene, alkyne, siloxy, cyano, hydroxyl, nitro, amine, acyl, cycloalkene or cycloalkyne;
A, X1 및 X2는 각각 독립적으로 C, O, S, Si, Ge, Sn, Pb, Se, 또는 Te 이고;A, X 1 and X 2 are each independently C, O, S, Si, Ge, Sn, Pb, Se, or Te;
m 및 n은 각각 독립적으로 0 내지 10의 정수이다.
m and n are each independently an integer of 0-10.
또한 본 발명은 Also,
(1) 스페이서 부분 (SP)을 포함하는 화합물을 유기용매에 녹인 후, 저온에서 n-부틸리튬과 반응시킨 다음, 이어서 같은 온도에서 할로겐이 치환된 전자 주개 화합물 (DO)과 반응시키는 단계; 및 (1) dissolving a compound comprising a spacer moiety (SP) in an organic solvent, and then reacting with n-butyllithium at low temperature, followed by reaction with an electron donor compound (DO) substituted with halogen at the same temperature; And
(2) 유기용매에 녹인 전자 받개 화합물 (AC)과 상기 단계 (1)에서 얻어진 화합물을 반응시키는 단계를 포함하는, 상기 화학식 1로 표시되는 염료의 제조방법을 제공한다.
(2) It provides a method for producing a dye represented by the formula (1) comprising the step of reacting the electron acceptor compound (AC) dissolved in the organic solvent and the compound obtained in the step (1).
또한 본 발명은 상기 화학식 1로 표시되는 화합물을 담지시킨 산화물 반도체 미립자를 포함하는 것을 특징으로 하는 염료증감 광전변환소자를 제공한다.
In another aspect, the present invention provides a dye-sensitized photoelectric conversion device comprising an oxide semiconductor fine particle carrying a compound represented by the formula (1).
또한 본 발명은 상기 염료증감 광전변환소자를 포함하는 것을 특징으로 하는 염료감응태양전지를 제공한다.
The present invention also provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.
본 발명의 염료 화합물은 염료감응태양전지 (DSSC)에 사용되어 종래의 염료보다 작은 밴드 갭 값을 나타내어 염료감응태양전지의 다양한 에너지 다이아그램에 맞춰 적응할 수 있고, 높은 몰흡광계수, 광전 변환효율 및 Jsc (단회로 광전류 밀도)을 나타내고 서로 다른 에너지 준위를 갖는 여러 광전극 층에 적용하여 태양전지의 효율을 크게 향상시킬 수 있다. 또한 고가의 칼럼을 사용하지 않고도 정제가 가능하여 염료 합성단가를 획기적으로 낮출 수 있다.
The dye compounds of the present invention can be used in dye-sensitized solar cells (DSSC), exhibiting a smaller band gap value than conventional dyes, and can be adapted to various energy diagrams of dye-sensitized solar cells, and have high molar extinction coefficient, photoelectric conversion efficiency and It can be applied to various photoelectrode layers which show J sc (short circuit photocurrent density) and have different energy levels, which can greatly improve the efficiency of the solar cell. In addition, purification can be performed without using an expensive column, thereby significantly lowering the cost of dye synthesis.
본 발명자들은, 특정 지방족 화합물을 전자 공여체 (DO) 로서 사용하고, 중간 연결부분 (SP)에는 작은 밴드 갭 값을 가지고, 몰흡광계수를 증가시키며 소자의 안정성을 증가시키기 위한 3개 이상의 헤테로사이클 고리 유닛을 도입하고, TiO2 개질에 잘 연결되어 전자 운반능력이 가장 좋은 시아노아크릴산을 포함하는 화합물을 전자 수용체 (AC)로 사용하는 새로운 유기염료 구조를 갖는 화학식 1로 표시되는 화합물을 산화물 반도체 미립자에 담지시켜 염료감응태양전지를 제조할 경우 광전기 변환효율, Jsc 및 몰흡광계수가 높아 기존 염료감응태양전지보다 우수한 효율을 나타냄을 확인하고 본 발명을 완성하게 되었다.We use certain aliphatic compounds as electron donors (DO), have a small band gap value at the intermediate linkage (SP), three or more heterocycle rings to increase the molar absorptivity and increase the stability of the device. The compound represented by the formula (1) having a new organic dye structure in which a unit is introduced and a compound containing cyanoacrylic acid, which is well connected to TiO 2 reforming and has the best electron transport ability, is used as an electron acceptor (AC). When the dye-sensitized solar cell is supported on the photoelectron conversion efficiency, the Jsc and the molar extinction coefficient are high, and thus, it is confirmed that the dye-sensitized solar cell exhibits better efficiency than the conventional dye-sensitized solar cell.
본 발명의 유기염료는 스페이서로서 3개 이상의 헤테로사이클 고리 유닛을 포함하는 화합물로서, 화학식 1로 표시되는 것을 특징으로 한다.The organic dye of the present invention is a compound comprising three or more heterocycle ring units as a spacer, characterized in that represented by the formula (1).
[화학식 1][Formula 1]
DO - Qm - B - Qn - ACDO-Qm-B-Qn-AC
상기 화학식 1에서,In Formula 1,
B는 
Q는 
DO는 지방족 화합물을 포함하는 전자 주개 그룹으로서, 바람직하게는 C1-50의 알킬, 이소알킬(가지형 알킬), 아릴, 알콕시, 알켄, 알킨, 실록시, 아민, 할로겐, 시아노, 하이드록실, 니트로, 아실, 아릴 또는 헤테로아릴기로 치환되거나 치환되지 않은 C1-50의 알킬, 아릴, 알콕시 또는 헤테로아릴이며;DO is an electron donor group containing an aliphatic compound, preferably C 1-50 alkyl, isoalkyl (branched alkyl), aryl, alkoxy, alkene, alkyne, siloxy, amine, halogen, cyano, hydroxyl C 1-50 alkyl, aryl, alkoxy or heteroaryl, optionally substituted with nitro, acyl, aryl or heteroaryl groups;
AC는 시아노아크릴산기를 포함하는 전자 받개 그룹으로서, 바람직하게는 하나 이상의 할로겐, C1-10 알킬, 또는 모노, 디 또는 트리페닐메틸로 치환되거나 치환되지 않은 시아노아크릴산기이고;AC is an electron acceptor group comprising a cyanoacrylic acid group, preferably a cyanoacrylic acid group which is optionally substituted with one or more halogen, C 1-10 alkyl, or mono, di or triphenylmethyl;
R1, R2, R3, R4, Y 및 Z는 각각 독립적으로 수소, 또는 헤테로 원자 또는 치환기로 치환되거나 치환되지 않은 1 내지 50의 탄소 수를 가지는 알킬, 이소알킬 (가지형 알킬), 아릴, 알콕시, 헤테로아릴, 알켄, 알킨, 실록시, 시아노, 하이드록실, 니트로, 아민, 아실, 시클로알켄 또는 시클로알킨이고;R 1 , R 2 , R 3 , R 4 , Y and Z are each independently hydrogen or alkyl having 1 to 50 carbon atoms, unsubstituted or substituted with a hetero atom or a substituent, isoalkyl (branched alkyl), Aryl, alkoxy, heteroaryl, alkene, alkyne, siloxy, cyano, hydroxyl, nitro, amine, acyl, cycloalkene or cycloalkyne;
A, X1 및 X2는 각각 독립적으로 C, O, S, Si, Ge, Sn, Pb, Se, 또는 Te 이고;A, X 1 and X 2 are each independently C, O, S, Si, Ge, Sn, Pb, Se, or Te;
m 및 n은 각각 독립적으로 0 내지 10의 정수이다.
m and n are each independently an integer of 0-10.
본 발명에서 사용할 수 있는 바람직한 전자 주개 그룹 (DO)의 구체적인 예는 다음과 같다:Specific examples of preferred electron donor groups (DO) that can be used in the present invention are as follows:
상기에서,In the above,
*는 결합부분이고;* Is a binding moiety;
R5, R6 및 R7은 각각 독립적으로 수소, 헤테로원자 또는 치환기로 치환되거나 치환되지 않은 1 내지 50의 탄소 수를 가지는 알킬, 이소알킬, 아릴, 알콕시, 헤테로아릴, 알켄, 알킨, 아민, 할로겐, 시아노, 하이드록실, 니트로, 아실, 실록시, 시클로알켄, 시클로알킨 또는 시클로헤테로알켄이다.
R 5 , R 6 and R 7 are each independently alkyl, isoalkyl, aryl, alkoxy, heteroaryl, alkene, alkyne, amine, having 1 to 50 carbon atoms, unsubstituted or substituted with hydrogen, heteroatoms or substituents; Halogen, cyano, hydroxyl, nitro, acyl, siloxy, cycloalkene, cycloalkyne or cycloheteroalkene.
또한 본 발명에서 사용할 수 있는 바람직한 전자 받개 그룹 (AC)의 구체적인 예는 다음과 같다:Specific examples of preferred electron acceptor groups (AC) which can also be used in the present invention are as follows:
상기에서,In the above,
W 및 Z는 각각 독립적으로 수소, 헤테로원자 또는 치환기로 치환되거나 치환되지 않은 1 내지 50의 탄소 수를 가지는 알킬, 이소알킬, 아릴, 알콕시, 헤테로아릴, 알켄, 알킨, 실록시, 시아노, 하이드록실, 니트로, 아실, 아민, 시클로알켄, 시클로알킨 또는 시클로헤테로알켄이고;W and Z each independently represent an alkyl, isoalkyl, aryl, alkoxy, heteroaryl, alkene, alkyne, siloxy, cyano, hydroxy having from 1 to 50 carbon atoms, optionally substituted with hydrogen, a heteroatom or a substituent Hydroxyl, nitro, acyl, amine, cycloalkene, cycloalkyne or cycloheteroalkene;
p 및 q는 각각 독립적으로 0 내지 10의 정수이며;p and q are each independently integers of 0 to 10;
S는 O, S, Se 또는 Te이다.
S is O, S, Se or Te.
또한 본 발명에서는 상기 DO와 Qm 사이, Qm과 B사이, B와 Qn사이, 또는 Qn과 AC 사이에 다음과 같은 구조식을 갖는 화합물(S1)을 추가로 포함할 수도 있다: In addition, the present invention may further include a compound (S1) having the following structural formula between the DO and Qm, between Qm and B, between B and Qn, or between Qn and AC:
또는 이들의 조합.Or combinations thereof.
상기 식에서,Where
R8, R9 및 R10은 각각 독립적으로 수소, 헤테로원자 또는 치환기로 치환되거나 치환되지 않은 1 내지 50의 탄소 수를 가지는 알킬, 이소알킬, 아릴, 알콕시, 헤테로아릴, 알켄, 알킨, 아민, 실록시, 시아노, 하이드록실, 니트로, 아실, 아민, 시클로알켄, 시클로알킨 또는 시클로헤테로알켄이고;R 8 , R 9 and R 10 are each independently alkyl, isoalkyl, aryl, alkoxy, heteroaryl, alkene, alkyne, amine, having 1 to 50 carbon atoms, unsubstituted or substituted with hydrogen, heteroatoms or substituents; Siloxy, cyano, hydroxyl, nitro, acyl, amine, cycloalkene, cycloalkyne or cycloheteroalkene;
X3 및 X4는 각각 독립적으로 O, S, Se 또는 Te이며;X 3 and X 4 are each independently O, S, Se or Te;
k는 0 내지 10의 정수이다.
k is an integer of 0-10.
일예로 본 발명의 유기염료는 하기 화학식 2 내지 7 중 어느 하나로 표시되는 것이 좋다.For example, the organic dye of the present invention may be represented by any one of the following Chemical Formulas 2 to 7.
[화학식 2][Formula 2]
DO - S1 - Qm - B - Qn - ACDO-S1-Qm-B-Qn-AC
[화학식 3](3)
DO - Qm - S1 - B - Qn - ACDO-Qm-S1-B-Qn-AC
[화학식 4][Formula 4]
DO - Qm - B - S1 - Qn - ACDO-Qm-B-S1-Qn-AC
[화학식 5][Chemical Formula 5]
DO - Qm - B - Qn - S1 - ACDO-Qm-B-Qn-S1-AC
[화학식 6][Formula 6]
DO - Qm - S1 - B - S1 - Qn - ACDO-Qm-S1-B-S1-Qn-AC
[화학식 7][Formula 7]
DO - S1 - Qm - S1 - B - S1 - Qn - ACDO-S1-Qm-S1-B-S1-Qn-AC
상기 식들에서,In the above equations,
R1, R2, R3, R4, Y, Z, A, X1, X2, AC, DO, S1, m 및 n은 상기에서 정의한 바와 같다.
R 1 , R 2 , R 3 , R 4 , Y, Z, A, X 1 , X 2 , AC, DO, S1, m and n are as defined above.
본 발명에 따른 상기 화학식 1의 화합물의 바람직한 예는 다음과 같다:Preferred examples of the compound of formula 1 according to the present invention are as follows:
[화학식 8][Formula 8]
[화학식 9][Chemical Formula 9]
[화학식 10][Formula 10]
[화학식 11][Formula 11]
[화학식 12][Chemical Formula 12]
[화학식 13][Chemical Formula 13]
[화학식 14][Formula 14]
[화학식 15][Formula 15]
[화학식 16][Chemical Formula 16]
[화학식 17][Chemical Formula 17]
[화학식 18][Chemical Formula 18]
[화학식 19][Formula 19]
[화학식 20][Chemical Formula 20]
[화학식 21][Chemical Formula 21]
[화학식 22][Formula 22]
[화학식 23](23)
[화학식 24]≪ EMI ID =
[화학식 25](25)
[화학식 26](26)
[화학식 27](27)
[화학식 28](28)
[화학식 29][Formula 29]
[화합물 30][Compound 30]
[화학식 31](31)
[화학식 32](32)
본 발명에 따른 화학식 1의 화합물은, (1) 스페이서 부분을 포함하는 화합물을 유기용매 (예를 들어, 테트라하이드로퓨란 (THF))에 녹인 후, 저온에서 n-부틸리튬과 반응시킨 다음, 이어서 같은 온도에서 할로겐이 치환된 전자 주개 화합물과 반응시키는 단계; 및 (2) 유기용매에 녹인 전자 받개 화합물과 상기 단계 (1)에서 얻어진 화합물을 반응시키는 단계를 포함하는 방법에 따라 제조될 수 있다.
Compound (1) according to the present invention comprises (1) dissolving a compound comprising a spacer moiety in an organic solvent (e.g., tetrahydrofuran (THF)), followed by reaction with n-butyllithium at low temperature, and then Reacting the halogen-substituted electron donor compound at the same temperature; And (2) reacting the electron acceptor compound dissolved in the organic solvent with the compound obtained in step (1).
구체적으로, 본 발명에 따른 화합물은 하기 반응식 1에 기재된 바와 같이,Specifically, the compounds according to the invention are as described in Scheme 1 below,
1) 하기 화학식 40의 화합물을 유기용매에 녹인 후, n-BuLi 및 트리부틸틴클로라이드와 차례로 반응시켜 하기 화학식 40-1의 화합물을 제조하는 단계;1) dissolving a compound of Formula 40 in an organic solvent and then reacting with n-BuLi and tributyltin chloride in order to prepare a compound of Formula 40-1;
2) 하기 화학식 41의 화합물을 유기용매에 녹인 후, 저온에서 n-BuLi 및 트리부틸틴클로라이드와 차례로 반응시켜 하기 화학식 41-1의 화합물을 제조한 다음, NBS (N-브로모숙신이미드)와 반응시켜 하기 화학식 41-2의 화합물을 제조하는 단계;2) The compound of formula 41 was dissolved in an organic solvent, and then reacted with n-BuLi and tributyltin chloride in turn at low temperature to prepare a compound of formula 41-1, followed by NBS (N-bromosuccinimide). Reacting with to prepare a compound of Formula 41-2;
3) 상기 단계 1) 및 2)에서 얻은 화학식 40-1 및 41-2의 화합물을 유기용매에 녹인 후, 스틸레 커플링 (Stille coupling) 반응시켜 하기 화학식 42의 화합물을 제조하는 단계; 및3) dissolving the compounds of Chemical Formulas 40-1 and 41-2 obtained in the above steps 1) and 2) in an organic solvent, and then carrying out a Stille coupling reaction to prepare a compound of Chemical Formula 42; And
4) 상기 단계 3)에서 얻은 화학식 42의 화합물을 CHCl3 또는 CH3CN 중에서 피페리딘 존재하에서 시아노아세트산과 반응시켜 하기 화학식 43-1의 화합물을 제조하는 단계를 포함하는 하기 반응식 1에 따른 방법에 따라 제조될 수 있다.
4) reacting the compound of formula 42 obtained in step 3) with cyanoacetic acid in the presence of piperidine in CHCl 3 or CH 3 CN to prepare a compound of formula 43-1 It may be prepared according to the method.
[반응식 1][Reaction Scheme 1]
또한, 본원 발명에 따른 화합물은 하기 반응식 2에 기재된 바와 같이,In addition, the compounds according to the present invention, as described in Scheme 2 below,
1) 상기 반응식 1의 방법에 따라 화학식 42의 화합물을 제조한 다음, 이를 유기용매에 녹인 다음, NaBH4와 반응시켜 화학식 42-1의 화합물을 제조한 다음, 유기용매 하에서 PPh3HBr와 환류반응시켜 화학식 42-2의 화합물을 제조하는 단계;1) preparing a compound of Chemical Formula 42 according to the method of Scheme 1, dissolving it in an organic solvent, reacting with NaBH 4 to prepare a compound of Chemical Formula 42-1, and refluxing with PPh 3 HBr in an organic solvent. To prepare a compound of formula 42-2;
2) 하기 화학식 44의 화합물을 유기용매 및 1,2-다이클로로에탄에 넣고 교반시킨 뒤, 저온에서 POCl3와 반응시켜 화학식 44-1의 화합물을 제조하는 단계;2) preparing a compound of Chemical Formula 44-1 by stirring the compound of Chemical Formula 44 in an organic solvent and 1,2-dichloroethane, and then reacting with POCl 3 at low temperature;
3) 상기 단계 1) 및 2)에서 얻은 화학식 42-2 및 44-1의 화합물을 포타슘 카보네이트 및 18-크라운-6와 반응시켜 하기 화학식 43-2의 화합물을 제조하는 단계; 및3) preparing a compound of formula 43-2 by reacting the compounds of formulas 42-2 and 44-1 obtained in steps 1) and 2) with potassium carbonate and 18-crown-6; And
4) 상기 단계 3)에서 얻은 화학식 43-2의 화합물을 CHCl3 또는 CH3CN 중에서 피페리딘 존재하에서 시아노아세트산과 반응시켜 하기 화학식 43-3의 화합물을 제조하는 단계를 포함하는 방법에 따라 제조될 수 있다.
4) reacting the compound of formula 43-2 obtained in step 3) with cyanoacetic acid in the presence of piperidine in CHCl 3 or CH 3 CN to prepare a compound of formula 43-3 Can be prepared.
[반응식 2]Scheme 2
또한 본원 발명에 따른 화합물은 하기 반응식 3에 기재된 바와 같이,In addition, the compounds according to the present invention are as described in Scheme 3 below,
1) 하기 화학식 41의 화합물을 유기용매에 녹인 후, 저온에서 n-BuLi 및 트리부틸틴클로라이드와 차례로 반응시켜 하기 화학식 31-3의 화합물을 제조하는 단계;1) dissolving a compound of Formula 41 in an organic solvent and then reacting with n-BuLi and tributyltin chloride in turn at low temperature to produce a compound of Formula 31-3;
2) 상기 단계 1)에서 얻은 화학식 41-3의 화합물과 하기 화학식 40의 화합물을 유기용매에 녹인 후, 스틸레 커플링 반응시켜 하기 화학식 42-3의 화합물을 제조하는 단계;2) preparing a compound of formula 42-3 by dissolving the compound of formula 41-3 obtained in step 1) and the compound of formula 40 in an organic solvent, followed by a stillet coupling reaction;
3) 상기 단계 2)에서 얻은 화학식 42-3의 화합물을 n-BuLi 및 2-이소프로폭시-4,4,5,5-테트라메틸-1,3,2-디옥사보로란과 반응시켜 하기 화학식 42-4의 화합물을 제조하는 단계;3) Reacting the compound of formula 42-3 obtained in step 2) with n-BuLi and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Preparing a compound of Formula 42-4;
4) 상기 단계 3)에서 얻은 화학식 42-4의 화합물에 하기 화학식 44-2의 화합물을 넣고, 디스틸반응시켜 하기 화학식 43-4의 화합물을 제조하는 단계; 및4) preparing a compound of formula 43-4 by adding a compound of formula 44-2 to a compound of formula 42-4 obtained in step 3) and performing a distillation reaction; And
5) 상기 단계 4)에서 얻은 화학식 43-4의 화합물을 CHCl3 또는 CH3CN 중에서 피페리딘 존재하에서 시아노아세트산과 반응시켜 하기 화학식 43-3의 화합물을 제조하는 단계를 포함하는 방법에 따라 제조될 수 있다.
5) reacting the compound of formula 43-4 obtained in step 4) with cyanoacetic acid in the presence of piperidine in CHCl 3 or CH 3 CN to prepare a compound of formula 43-3 Can be prepared.
[반응식 3]Scheme 3
또한 본원 발명에 따른 화합물은 하기 반응식 4에 기재된 바와 같이,In addition, the compounds according to the present invention are as described in Scheme 4 below,
1) 상기 반응식 1의 방법에 따라 하기 화학식 40-1의 화합물을 제조하는 단계;1) preparing a compound of Formula 40-1 according to the method of Scheme 1 above;
2) 하기 화학식 31의 화합물을 NBS와 반응시켜 하기 화학식 41-4의 화합물을 제조한 다음, 하기 화학식 40-2의 화합물과 스즈끼 커플링 반응시켜 하기 화학식 42-5의 화합물을 제조하는 단계;2) preparing a compound represented by Chemical Formula 41-5 by reacting the compound represented by Chemical Formula 31 with NBS, followed by Suzuki coupling with the compound represented by Chemical Formula 40-2;
3) 상기 단계 2)에서 얻은 화학식 42-5의 화합물을 NBS와 반응시켜 하기 화학식 42-6의 화합물을 제조한 다음, 상기 단계 1)에서 얻은 화학식 40-1의 화합물과 스틸레 커플링 반응시켜 하기 화학식 42-7의 화합물을 제조하고, 이를 NBS와 반응시켜 하기 화학식 42-8의 화합물의 제조하는 단계;3) The compound of formula 42-5 obtained in step 2) is reacted with NBS to prepare a compound of formula 42-6, and then subjected to a stille coupling reaction with the compound of formula 40-1 obtained in step 1). Preparing a compound of Formula 42-7 and reacting it with NBS to prepare a compound of Formula 42-8;
4) 상기 단계 3)에서 얻은 화학식 42-8의 화합물을 하기 화학식 44-3의 화합물과 스즈끼 커플링 반응시켜 하기 화학식 43-5의 화합물을 제조하는 단계; 및4) preparing a compound of formula 43-5 by Suzuki coupling reaction of the compound of formula 42-8 obtained in step 3) with a compound of formula 44-3; And
5) 상기 단계 4)에서 얻은 화학식 43-5의 화합물을 CHCl3 또는 CH3CN 중에서 피페리딘 존재하에서 시아노아세트산과 반응시켜 하기 화학식 43-6의 화합물을 제조하는 단계를 포함하는 방법에 따라 제조될 수 있다.
5) reacting the compound of formula 43-5 obtained in step 4) with cyanoacetic acid in the presence of piperidine in CHCl 3 or CH 3 CN to prepare a compound of formula 43-6 Can be prepared.
[반응식 4][Reaction Scheme 4]
상기 화학식 1의 화합물을 제조하는데 출발물질로서 사용되는 전자 주개 (DO) 및 전자 받개 화합물 (AC)은 각각의 전자 주개 및 전자 받개 그룹의 종류에 따라 통상적인 방법으로 제조할 수 있다.
The electron donor (DO) and electron acceptor compound (AC) used as starting materials for preparing the compound of Formula 1 may be prepared by a conventional method according to the type of each electron donor and electron acceptor group.
본 발명에 따른 화학식 1의 복소다환 화합물은 적정한 광흡수 파장 및 형광 파장을 가지고 있고, 발광 강도가 높은 것 등의 제성능이 뛰어난 염료로서 염료감응 태양전지용 염료로 매우 유용하다.
The heteropolycyclic compound of the general formula (1) according to the present invention has a suitable light absorption wavelength and fluorescence wavelength, and is very useful as a dye for solar cells having a high dyeing performance such as high emission intensity.
또한 본 발명은 염료증감 광전변환소자를 제공하는 바, 상기 염료증감 광전변환소자는 산화물 반도체 미립자에 상기 화학식 1로 표시되는 염료를 담지시킨 것을 특징으로 한다. 본 발명의 염료증감 광전변환소자는 상기 화학식 1로 표시되는 염료를 사용하는 것 이외에 종래 염료를 이용하여 태양전지용 염료증감 광전변환소자를 제조하는 방법들이 적용될 수 있음은 물론이며, 구체적인 일예로 대한민국공개특허공보 제10-2009-38377호 (출원인 동진쎄미켐(주))에 기재된 방법들이 적용될 수 있으며, 바람직하게는 본 발명의 염료증감 광전변환소자는 산화물 반도체 미립자를 이용해서 기판상에 산화물 반도체의 박막을 제조하고, 이어서 상기 박막에 본 발명의 염료를 담지시킨 것이 좋다.
In addition, the present invention provides a dye-sensitized photoelectric conversion device, the dye-sensitized photoelectric conversion device is characterized in that the dye represented by the formula (1) on the oxide semiconductor fine particles. As a dye-sensitized photoelectric conversion device of the present invention, in addition to using the dye represented by Chemical Formula 1, methods for manufacturing dye-sensitized photoelectric conversion devices for solar cells using conventional dyes may be applied. The methods described in Patent Publication No. 10-2009-38377 (Dongjin Semichem Co., Ltd.) can be applied, and preferably the dye-sensitized photoelectric conversion device of the present invention is a thin film of an oxide semiconductor on a substrate using oxide semiconductor fine particles. It is preferable that the dye of the present invention is supported on the thin film.
또한 본 발명은 상기 염료감응 광전변환소자를 포함하는 것을 특징으로 하는 염료감응태양전지를 제공하는 바, 상기 화학식 1로 표시되는 염료를 담지시킨 산화물 반도체 미립자를 이용한 염료증감 광전변환소자를 사용하는 것 이외에 종래 광전변환소자를 사용하여 태양전지를 제조하는 통상의 방법들이 적용될 수 있음은 물론이며, 구체적인 예로 상기 산화물 반도체 미립자에 화학식 1로 표시되는 염료를 담지시킨 광전변환소자 전극 (음극), 대전극 (양극), 산화환원 전해질, 정공수송 재료 또는 p형 반도체 등으로 구성될 수 있다.
In another aspect, the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device, using a dye-sensitized photoelectric conversion device using the oxide semiconductor fine particles carrying the dye represented by the formula (1) In addition, conventional methods of manufacturing a solar cell using a conventional photoelectric conversion device may be applied, and in particular, a photoelectric conversion device electrode (cathode) and a counter electrode supporting the dye represented by Formula 1 on the oxide semiconductor fine particles (Anode), a redox electrolyte, a hole transport material, a p-type semiconductor, or the like.
이하에서 본 발명을 실시예에 의거하여 보다 구체적으로 설명한다. 단, 이들 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명이 이들만으로 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples. However, these Examples are only for illustrating the present invention, the present invention is not limited to these.
실시예 1: 화학식 28의 화합물의 제조Example 1 Preparation of a Compound of Formula 28
[반응식 5]Scheme 5
<1-1> 화학식 28-1의 화합물의 제조<1-1> Preparation of a Compound of Formula 28-1
N-(4-브로모페닐)-N-(9,9-디메틸-9H-플루오렌-3-일)-9,9-디메틸-9H-플루오렌-3-아민 (9.21 g, 16.55 mmol)을 2-(트리부틸스태닐)-3,4-(에틸렌디옥시)티오펜 (10.70 g, 24.82 mmol) 및 Pd(PPh3)2Cl2 (1.16 g, 1.65 mmol)와 함께 교반기에 넣고 무수 톨루엔 (150 ㎖)에 녹인 뒤, 120℃, 아르곤 분위기에서 16시간 동안 반응시켜 N-(4-(2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)페닐)-N-(9,9-디메틸-9H-플루오렌-3-일)-9,9-디메틸-9H-플루오렌-3-아민을 합성하였다.
N- (4-bromophenyl) -N- (9,9-dimethyl-9H-fluoren-3-yl) -9,9-dimethyl-9H-fluorene-3-amine (9.21 g, 16.55 mmol) Was added to the stirrer with 2- (tributylstannyl) -3,4- (ethylenedioxy) thiophene (10.70 g, 24.82 mmol) and Pd (PPh 3 ) 2 Cl 2 (1.16 g, 1.65 mmol) After dissolving in toluene (150 ml), the mixture was reacted for 16 hours at 120 ° C. in an argon atmosphere, followed by N- (4- (2,3-dihydrothieno [3,4-b] [1,4] dioxine-5 -Yl) phenyl) -N- (9,9-dimethyl-9H-fluoren-3-yl) -9,9-dimethyl-9H-fluoren-3-amine was synthesized.
<1-2> 화학식 28-2의 화합물의 제조<1-2> Preparation of a compound of Formula 28-2
상기에서 얻은 화합물 28-1 (9.26 g, 15 mmol)을 무수 THF 50 ㎖에 녹인 후 -78℃에서 1.6 M n-BuLi (11.25 ㎖, 18 mmol)을 서서히 적가하여 1시간 동안 저온 교반하였다. 다시 여기에 트리부틸틴 클로라이드 (3.58 g, 18 mmol)를 -78℃에서 서서히 적가한 후 1시간 동안 저온에서 교반하고, 추가로 상온에서 6시간 동안 교반하여 N-(9,9-디메틸-9H-플루오렌-3-일)-9,9-디메틸-N-(4-(7-(트리부틸스태닐)-2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)페닐)-9H-플루오렌-3-아민을 합성하였다.
Compound 28-1 (9.26 g, 15 mmol) obtained above was dissolved in 50 mL of anhydrous THF, and 1.6 M n-BuLi (11.25 mL, 18 mmol) was slowly added dropwise at −78 ° C. and stirred at low temperature for 1 hour. Again tributyltin chloride (3.58 g, 18 mmol) was slowly added dropwise at -78 ℃ and stirred for 1 hour at low temperature, and further stirred at room temperature for 6 hours to give N- (9,9-dimethyl-9H -Fluoren-3-yl) -9,9-dimethyl-N- (4- (7- (tributylstannyl) -2,3-dihydrothieno [3,4-b] [1,4] Dioxin-5-yl) phenyl) -9H-fluorene-3-amine was synthesized.
<1-3> 화학식 28-3의 화합물의 제조<1-3> Preparation of the compound of Formula 28-3
4,4-디헥실-2,6-디메틸-4H-실롤로[3,2-b:4,5-b']디티오펜 (3.90 g, 10 mmol)을 THF에 녹인 후, n-BuLi (7.5 ㎖, 12 mmol)을 -78℃에서 아르곤 하에서 첨가하였다. 3시간 후에, 여기에 DMF (0.05 g, 0.7 mmol)를 아르곤 하에서 첨가하고 5% KOH로 세척하였다. 반응용액을 황산마그네슘으로 건조하고 용매를 제거하여 4,4-디헥실-6-메틸-4H-실롤[3,2-b:4,5-b']디티오펜-2-카브알데하이드를 합성하였다.
4,4-Dihexyl-2,6-dimethyl-4H-silolo [3,2-b: 4,5-b '] dithiophene (3.90 g, 10 mmol) was dissolved in THF, followed by n-BuLi ( 7.5 mL, 12 mmol) was added at -78 ° C under argon. After 3 hours, DMF (0.05 g, 0.7 mmol) was added thereto under argon and washed with 5% KOH. The reaction solution was dried over magnesium sulfate and the solvent was removed to synthesize 4,4-dihexyl-6-methyl-4H-silol [3,2-b: 4,5-b '] dithiophene-2-carbaldehyde. .
<1-4> 화학식 28-4의 화합물의 제조<1-4> Preparation of a Compound of Formula 28-4
상기에서 얻은 화합물 28-3 (2.02 g, 5 mmol)을 DMF (20 ㎖)에 녹인 후 NBS (0.28 g, 5 mmol)를 0℃ 에서 적하하여 실온에서 4시간 동안 반응시켰다. 이 혼합용액에 물 (30 ㎖)과 염수를 첨가한 후, 유기층을 분리하여 황산마그네슘으로 건조하였다. 용매를 진공 하에서 제거한 후 얻어진 고형물을 크로마토그래피로 정제하여 6-브로모-4,4-디헥실-4H-실롤[3,2-b:4,5-b']디티오펜-2-카브알데하이드을 합성하였다.
Compound 28-3 (2.02 g, 5 mmol) obtained above was dissolved in DMF (20 mL), and NBS (0.28 g, 5 mmol) was added dropwise at 0 ° C and reacted at room temperature for 4 hours. Water (30 mL) and brine were added to the mixed solution, and the organic layer was separated and dried over magnesium sulfate. The solvent was removed under vacuum and the resulting solid was purified by chromatography to give 6-bromo-4,4-dihexyl-4H-silol [3,2-b: 4,5-b '] dithiophene-2-carbaldehyde. Synthesized.
<1-5> 화학식 28-5의 화합물의 제조<1-5> Preparation of a Compound of Formula 28-5
상기에서 얻은 화합물 28-2 (2.38 g, 2.63 mmol)와 28-4 (1.23 g, 2.63 mmol)를 톨루엔에 녹인 후, 스틸레 커플링 반응을 하고, 반응이 끝난 후 메틸렌클로라이드와 물을 사용하여 유기층을 추출 한 다음, 증발을 통하여 건조 후 컬럼 정제하여 7-(7-(4-(비스(9,9-디메틸-9H-플루오렌-3-일)아미노)페닐)-2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)-5,5-디메틸-5H-디벤조[b,d]실롤-2-카브알데하이드를 합성하였다.
Compound 28-2 (2.38 g, 2.63 mmol) and 28-4 (1.23 g, 2.63 mmol) obtained above were dissolved in toluene, and then subjected to a stlelet coupling reaction. After the reaction was completed, methylene chloride and water were used. The organic layer was extracted, dried through evaporation, and then purified by column to obtain 7- (7- (4- (bis (9,9-dimethyl-9H-fluoren-3-yl) amino) phenyl) -2,3-di Hydrothieno [3,4-b] [1,4] dioxin-5-yl) -5,5-dimethyl-5H-dibenzo [b, d] silol-2-carbaldehyde was synthesized.
<1-6> 화학식 28의 화합물의 제조<1-6> Preparation of a Compound of Formula 28
상기에서 얻은 화합물 28-5 (1.20 g, 1.2 mmol)를 시아노아세트산 (0.2 g, 2.4 mmol) 및 피페리딘 (0.24 ㎖, 2.4 mmol)과 함께 아세토니트릴 (30 ㎖)에 녹인 후 4시간 동안 환류시키면서 교반하였다. 교반이 끝난 후 에틸렌클로라이드와 물을 사용하여 유기층을 추출한 다음, 증발 건조시키고 컬럼 정제하여 최종 염료 (E)-3-(6-(7-(4-(비스(9,9-디메틸-9H-플루오렌-3-일)아미노)페닐)-2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)-4,4-디헥실-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)-2-시아노아크릴산을 합성하였다.
Compound 28-5 (1.20 g, 1.2 mmol) obtained above was dissolved in acetonitrile (30 mL) with cyanoacetic acid (0.2 g, 2.4 mmol) and piperidine (0.24 mL, 2.4 mmol) for 4 hours. Stirring at reflux. After stirring, the organic layer was extracted with ethylene chloride and water, and then evaporated to dryness and column purified to give the final dye (E) -3- (6- (7- (4- (bis (9,9-dimethyl-9H-). Fluoren-3-yl) amino) phenyl) -2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) -4,4-dihexyl-4H-silol [3,2-b: 4,5-b '] dithiophen-2-yl) -2-cyanoacrylic acid was synthesized.
실시예 2: 화학식 21의 화합물의 제조Example 2: Preparation of Compound of Formula 21
[반응식 6][Reaction Scheme 6]
<2-1> 화학식 21-1의 화합물의 제조<2-1> Preparation of a compound of formula 21-1
상기 실시예 <1-1>과 동일한 방법으로 N-(4-(2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)페닐)-N-(9,9-디메틸-9H-플루오렌-3-일)-9,9-디메틸-9H-플루오렌-3-아민을 합성하였다.
N- (4- (2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) phenyl) -N- in the same manner as in Example <1-1> (9,9-dimethyl-9H-fluoren-3-yl) -9,9-dimethyl-9H-fluoren-3-amine was synthesized.
<2-2> 화학식 21-2의 화합물의 제조<2-2> Preparation of a compound of Formula 21-2
상기 실시예 <1-2>와 동일한 방법으로 N-(9,9-디메틸-9H-플루오렌-3-일)-9,9-디메틸-N-(4-(7-(트리부틸스태닐)-2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)페닐)-9H-플루오렌-3-아민을 합성하였다.
N- (9,9-dimethyl-9H-fluoren-3-yl) -9,9-dimethyl-N- (4- (7- (tributylstannyl) in the same manner as in Example <1-2> ) -2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) phenyl) -9H-fluoren-3-amine was synthesized.
<2-3> 화학식 21-3의 화합물의 제조<2-3> Preparation of the compound of formula 21-3
135℃ 온도 조건 하에서 (4',4-디메틸-[1,1'-bi페닐]-2-일)디메틸실란 (3.6 g, 15 mmol), RhCl(PPh3)3 (0.58 mg,0.075 mmol) 및 1,4-디옥산 (15 ㎖)을 밀폐된 반응기 안에서 15분 동안 교반시킨 후, 컬럼 정제하여 3,5,5,7-테트라메틸-5H-디벤조[b,d]실롤을 합성하였다.
(4 ', 4-dimethyl- [1,1'-biphenyl] -2-yl) dimethylsilane (3.6 g, 15 mmol), RhCl (PPh 3 ) 3 (0.58 mg, 0.075 mmol) under 135 ° C temperature conditions And 1,4-dioxane (15 mL) was stirred in a closed reactor for 15 minutes, followed by column purification to synthesize 3,5,5,7-tetramethyl-5H-dibenzo [b, d] silol. .
<2-4> 화학식 21-4의 화합물의 제조<2-4> Preparation of a Compound of Formula 21-4
상기에서 얻은 화합물 21-3 (1.66 g, 7 mmol)을 DMF (50 ㎖) 및 1,2-디클로로에탄 (30 ㎖)과 함께 교반기에 넣고 교반시킨 뒤, 0℃ 에서 포스포러스 클로라이드 옥사이드 (2.29 g, 15 mmol)를 적가하여, 135℃에서 15분 동안 반응시켰다. 상기 혼합물을 디스틸하여 모든 용매를 제거한 후, 컬럼으로 분리하여 5,5,7-트리메틸-5H-디벤조[b,d]실롤-3-카브알데하이드를 합성하였다.
Compound 21-3 (1.66 g, 7 mmol), obtained above, was mixed with DMF (50 mL) and 1,2-dichloroethane (30 mL) in a stirrer and stirred, followed by phosphorus chloride oxide (2.29 g) at 0 ° C. , 15 mmol) was added dropwise and reacted at 135 ° C. for 15 minutes. The mixture was distilled to remove all solvents and then separated by column to synthesize 5,5,7-trimethyl-5H-dibenzo [b, d] silol-3-carbaldehyde.
<2-5> 화학식 21-5의 화합물의 제조<2-5> Preparation of a Compound of Formula 21-5
상기에서 얻은 화합물 21-4 (1.26 g, 5 mmol)를 DMF (50 ㎖)에 녹인 후, NBS (0.88 g, 5 mmol)를 0℃에서 적하하고 실온에서 4시간 동안 혼합하였다. 이 혼합용액에 물과 염수를 첨가한 후, 유기층을 분리하여 건조시킨 후 컬럼 정제하여 7-브로모-5,5-디메틸-5H-디벤조[b,d]실롤-3-카브알데하이드를 합성하였다.
Compound 21-4 (1.26 g, 5 mmol) obtained above was dissolved in DMF (50 mL), and NBS (0.88 g, 5 mmol) was added dropwise at 0 ° C, and mixed for 4 hours at room temperature. Water and brine were added to the mixed solution, the organic layer was separated, dried and purified by column to synthesize 7-bromo-5,5-dimethyl-5H-dibenzo [b, d] silol-3-carbaldehyde. It was.
<2-6> 화학식 21-6의 화합물의 제조<2-6> Preparation of a Compound of Formula 21-6
상기에서 얻은 화합물 21-2 (4.08 g, 4.5 mmol)와 21-5 (1.58 g, 5 mmol)를 톨루엔에 녹인 후, 스틸레 커플링 반응시키고, 반응이 끝난 후 메틸렌클로라이드 와 물을 사용하여 유기층을 추출하고 증발을 통하여 건조 후 컬럼 정제하여 7-(7-(4-(비스(9,9-디메틸-9H-플루오렌-3-일)아미노)페닐)-2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)-5,5-디메틸-5H-디벤조[b,d]실롤-3-카브알데하이드를 합성하였다.
Compound 21-2 (4.08 g, 4.5 mmol) and 21-5 (1.58 g, 5 mmol) obtained above were dissolved in toluene, and then subjected to stillet coupling reaction. After completion of the reaction, an organic layer using methylene chloride and water was used. Extracted, dried through evaporation and column purified to give 7- (7- (4- (bis (9,9-dimethyl-9H-fluoren-3-yl) amino) phenyl) -2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) -5,5-dimethyl-5H-dibenzo [b, d] silol-3-carbaldehyde was synthesized.
<2-7> 화학식 21의 화합물의 제조<2-7> Preparation of Compound of Formula 21
상기에서 얻은 화합물 21-6 (1.28 g ,1.5 mmol)을 시아노아세트산 (0.25 g, 3 mmol) 및 피페리딘 (0.14 ㎖, 1.5 mmol)과 함께 아세토니트릴 (50 ㎖)에 녹인 후 4시간 동안 환류시키면서 교반하였다. 교반이 끝난 후 반응용액을 냉각시키고 메틸렌클로라이드와 물을 사용하여 유기층을 추출하고 증발 건조시킨 뒤 컬럼 정제하여 최종 염료 (Z)-3-(7-(7-(4-(비스(9,9-디메틸-9H-플루오렌-3-일)아미노)페닐)-2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)-5,5-디메틸-5H-디벤조[b,d]실롤-3-일)-2-시아노아크릴산을 합성하였다.
Compound 21-6 (1.28 g, 1.5 mmol) obtained above was dissolved in acetonitrile (50 mL) with cyanoacetic acid (0.25 g, 3 mmol) and piperidine (0.14 mL, 1.5 mmol) for 4 hours. Stirring at reflux. After stirring, the reaction solution was cooled, the organic layer was extracted with methylene chloride and water, evaporated to dryness, and then purified by column to obtain the final dye (Z) -3- (7- (7- (4- (bis (9,9,9,9) -Dimethyl-9H-fluoren-3-yl) amino) phenyl) -2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) -5,5-dimethyl -5H-dibenzo [b, d] silol-3-yl) -2-cyanoacrylic acid was synthesized.
실시예 3: 화학식 29의 화합물의 제조Example 3: Preparation of Compound of Formula 29
[반응식 7][Reaction Scheme 7]
<3-1> 화학식 29-1의 화합물의 제조<3-1> Preparation of a compound of formula 29-1
1-브로모-4-(브로모메틸)벤젠 (5 g, 20 mmol)을 트리에틸 포스파이트 (25 g, 150 mmol)와 함께 교반기에 넣고 2시간 동안 120℃에서 반응시켜 디에틸 4-브로모벤질포스포네이트를 합성하였다.
1-Bromo-4- (bromomethyl) benzene (5 g, 20 mmol) was added to the stirrer with triethyl phosphite (25 g, 150 mmol) and reacted at 120 ° C. for 2 hours to diethyl 4-bromine. Mobenzylphosphonates were synthesized.
<3-2> 화학식 29-2의 화합물의 제조<3-2> Preparation of a Compound of Formula 29-2
상기에서 얻은 화합물 29-1 (6.74 g, 20 mmol), 벤조페논 (5.13 g, 29.16 mmol) 및 포타슘 tert-부톡사이드 (3.27 g, 29.16 mmol)를 반응기에 넣고 THF 50 ㎖에 녹여 4시간 동안 120℃에서 반응시켜 (2-(4-브로모페닐)에텐-1,1-디일)디벤젠을 합성하였다.
Compound 29-1 (6.74 g, 20 mmol), benzophenone (5.13 g, 29.16 mmol) and potassium tert-butoxide (3.27 g, 29.16 mmol) obtained in the above were added to a reactor and dissolved in 50 mL of THF for 120 hours. The reaction was carried out at 占 폚 to synthesize (2- (4-bromophenyl) ethene-1,1-diyl) dibenzene.
<3-3> 화학식 29-3의 화합물의 제조<3-3> Preparation of the compound of formula 29-3
상기에서 얻은 화합물 29-2 (5.02 g ,15 mmol)를 무수 THF (50 ㎖)에 녹인 후 -78℃에서 1.6 M n-BuLi (11.25 ㎖, 18 mmol)을 서서히 적가하여 1시간 동안 저온 교반하였다. 다시 여기에 트리부틸틴 클로라이드 (6.10 g, 18 mmol)를 -78℃에서 서서히 적가한 후 1시간 동안 저온에서 교반하고 추가로 상온에서 6시간 동안 교반하여 트리부틸(4-(2,2-디페닐비닐)페닐)스태난을 합성하였다.
Compound 29-2 (5.02 g, 15 mmol) obtained above was dissolved in anhydrous THF (50 mL), and 1.6 M n-BuLi (11.25 mL, 18 mmol) was slowly added dropwise at −78 ° C., followed by low temperature stirring for 1 hour. . Again tributyltin chloride (6.10 g, 18 mmol) was slowly added dropwise at -78 ℃ and stirred for 1 hour at low temperature and further stirred at room temperature for 6 hours to give tributyl (4- (2,2-di Phenylvinyl) phenyl) stanan was synthesized.
<3-4> 화학식 29-4의 화합물의 제조<3-4> Preparation of a Compound of Formula 29-4
1,2-디클로로에탄 (30 ㎖)에 2,6-디메틸-4,4-디페닐-4H-실롤[3,2-b:4,5-b']디티오펜 (6.54 g, 12 mmol)과 DMF (1.05 g, 14.4 mmol)를 넣고 교반시킨 뒤, 저온 (0℃)에서 포스포러스 클로라이드 옥사이드 (2.20 g, 14.4 mmol)를 적가한 후, 80℃ 에서 4시간 동안 반응시켜 6-메틸-4,4-디페닐-4H-실롤[3,2-b:4,5-b']디티오펜-2-카브알데하이드를 합성하였다.
2,6-dimethyl-4,4-diphenyl-4H-silol [3,2-b: 4,5-b '] dithiophene (6.54 g, 12 mmol) in 1,2-dichloroethane (30 mL) And DMF (1.05 g, 14.4 mmol) was added and stirred, followed by dropwise addition of phosphorus chloride oxide (2.20 g, 14.4 mmol) at low temperature (0 ° C.), followed by reaction at 80 ° C. for 4 hours to give 6-methyl-4 , 4-diphenyl-4H-silol [3,2-b: 4,5-b '] dithiophene-2-carbaldehyde was synthesized.
<3-5> 화학식 29-5의 화합물의 제조<3-5> Preparation of a Compound of Formula 29-5
상기에서 얻은 화합물 29-4 (3.88 g, 10 mmol)를 DMF (30 ㎖)에 녹인 후 NBS (2.13 g, 12 mmol)를 0℃ 에서 적하하고 실온에서 4시간 동안 반응시켜 6-브로모-4,4-디페닐-4H-실롤[3,2-b:4,5-b']디티오펜-2-카브알데하이드를 합성하였다.
Compound 29-4 (3.88 g, 10 mmol) obtained above was dissolved in DMF (30 mL), NBS (2.13 g, 12 mmol) was added dropwise at 0 ° C, and reacted at room temperature for 4 hours to give 6-bromo-4. , 4-diphenyl-4H-silol [3,2-b: 4,5-b '] dithiophene-2-carbaldehyde was synthesized.
<3-6> 화학식 29-6의 화합물의 제조<3-6> Preparation of a Compound of Formula 29-6
상기에서 얻은 화합물 29-3 (5.45 g, 10 mmol)과 29-5 (4.53 g, 10 mmol)를 톨루엔에 녹인 후, 스틸레 커플링 반응시켰다. 반응이 끝난 후 메틸렌클로라이드 와 물을 사용하여 유기층을 추출한 다음, 증발을 통하여 건조 후 컬럼 정제하여 (6-(4-(2,2-디페닐비닐)페닐)-4,4-디페닐-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)카브알데하이드(6-(4-(2,2-diphenylvinyl)phenyl)-4,4-diphenyl-4H-silolo[3,2-b:4,5-b'] dithiophene-2-carbaldehyde)를 합성하였다.
Compound 29-3 (5.45 g, 10 mmol) and 29-5 (4.53 g, 10 mmol) obtained above were dissolved in toluene, and then subjected to a stille coupling reaction. After the reaction, the organic layer was extracted with methylene chloride and water, dried through evaporation and purified by column (6- (4- (2,2-diphenylvinyl) phenyl) -4,4-diphenyl-4H. -Silol [3,2-b: 4,5-b '] dithiophen-2-yl) carbaldehyde (6- (4- (2,2-diphenylvinyl) phenyl) -4,4-diphenyl-4H-silolo [3,2-b: 4,5-b '] dithiophene-2-carbaldehyde) was synthesized.
<3-7> 화학식 29-7의 화합물의 제조<3-7> Preparation of a Compound of Formula 29-7
상기에서 얻은 화합물 29-6 (4.4 g, 7 mmol)을 THF과 에탄올에 녹이고 소듐 보로하이드라이드를 적가한 후, 상온에서 2시간 교반하여 (6-(4-(2,2-디페닐비닐)페닐)-4,4-디페닐-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)메탄올을 합성하였다.
Compound 29-6 (4.4 g, 7 mmol) obtained above was dissolved in THF and ethanol, and sodium borohydride was added dropwise, followed by stirring at room temperature for 2 hours to give (6- (4- (2,2-diphenylvinyl)). Phenyl) -4,4-diphenyl-4H-silol [3,2-b: 4,5-b '] dithiophen-2-yl) methanol was synthesized.
<3-8> 화학식 29-8의 화합물의 제조<3-8> Preparation of a Compound of Formula 29-8
상기에서 얻은 화합물 29-7 (3.15 mg, 5 mmol)과 PPh3HBr (2.05 g, 6 mmol) 을 100 ㎖의 클로로포름에 녹인 뒤, 2시간 동안 환류시키며 교반하였다. 그 후 용매를 제거하고 에테르로 재결정하여 브로모((6-(4-(2,2-디페닐비닐)페닐)-4,4-디페닐-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)메틸)트리페닐포스포란을 합성하였다.Compound 29-7 (3.15 mg, 5 mmol) and PPh 3 HBr (2.05 g, 6 mmol) obtained above were dissolved in 100 mL of chloroform, and then stirred under reflux for 2 hours. The solvent was then removed and recrystallized from ether to give bromo ((6- (4- (2,2-diphenylvinyl) phenyl) -4,4-diphenyl-4H-silol [3,2-b: 4, 5-b '] dithiophen-2-yl) methyl) triphenylphosphoran was synthesized.
<3-9> 화학식 29-9의 화합물의 제조<3-9> Preparation of a compound of formula 29-9
3,4-디브로모티오펜 (1.20 g, 8.89 mmol)을 0℃에서 Et2NH (10 ㎖)에 천천히 적가하여 녹인 후, PdCl2(PPh3)2 (0.104 g 0.148 mmol) 및 CuI (0.141 g, 0.740 mmol)를 함께 넣고 교반한 다음, 같은 온도에서 옥트-1-인 (0.571 g, 8.15 mmol)을 천천히 떨어뜨리고 4시간 동안 반응시켰다. 반응이 끝난 후 물과 디에틸 에테르를 사용하여 유기층을 추출한 후 건조하고 컬럼 정제하여 3-브로모-4-(옥트-1-인-1-일)티오펜을 합성하였다.
3,4-dibromothiophene (1.20 g, 8.89 mmol) was slowly added dropwise to Et 2 NH (10 mL) at 0 ° C. to dissolve, followed by PdCl 2 (PPh 3 ) 2 (0.104 g 0.148 mmol) and CuI (0.141). g, 0.740 mmol) were added together and stirred, followed by slowly dropping oct-1-yne (0.571 g, 8.15 mmol) at the same temperature and reacting for 4 hours. After the reaction, the organic layer was extracted with water and diethyl ether, dried and purified by column to synthesize 3-bromo-4- (oct-1-yn-1-yl) thiophene.
<3-10> 화학식 29-10의 화합물의 제조<3-10> Preparation of a Compound of Formula 29-10
상기에서 얻은 화합물 29-9 (2.16 g, 8 mmol)를 CuO 및 Na2S.9H2O와 함께 N-메틸피롤리디논에 녹인 후, 180℃에서 4시간 동안 반응시켜 2-헥실티에노[3,4-b]티오펜을 합성하였다.
Compound 29-9 (2.16 g, 8 mmol) obtained above was dissolved in N-methylpyrrolidinone with CuO and Na 2 S.9H 2 O, and then reacted at 180 ° C. for 4 hours to give 2-hexylthieno [ 3,4-b] thiophene was synthesized.
<3-11> 화학식 29-11의 화합물의 제조<3-11> Preparation of a Compound of Formula 29-11
상기에서 얻은 화합물 29-10 (0.89 g, 4 mmol)을 DMF (0.35 g, 4.8 mmol)와 함께 1,2-디클로로에탄 (30 ㎖)에 넣고 교반시킨 뒤, 저온(-78℃)에서 포스포러스 클로라이드 옥사이드 (0.74 g, 4.8 mmol)를 적가하고 80℃ 에서 4시간 동안 반응시켜 2-헥실티에노[3,4-b]티오펜-4,6-디카브알데하이드를 합성하였다.
Compound 29-10 (0.89 g, 4 mmol) obtained above was added to 1,2-dichloroethane (30 mL) with DMF (0.35 g, 4.8 mmol) and stirred, followed by phosphorus at low temperature (-78 ° C). Chloride oxide (0.74 g, 4.8 mmol) was added dropwise and reacted at 80 ° C. for 4 hours to synthesize 2-hexylthieno [3,4-b] thiophene-4,6-dicarbaldehyde.
<3-12> 화학식 29-12의 화합물의 제조<3-12> Preparation of a Compound of Formula 29-12
상기에서 얻은 화합물 29-8 (2.86 g, 3 mmol)과 29-11 (0.84 g, 3 mmol)을 DMF에 녹인 후, 포타슘 카보네이트와 18-크라운-6을 넣고 120℃에서 20시간 동안 교반하여 (E)-4-(2-(6-(4-(2,2-디페닐비닐)페닐)-4,4-디페닐-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)비닐)-2-헥실티에노[3,4-b]티오펜-6-카브알데하이드를 합성하였다.
Compound 29-8 (2.86 g, 3 mmol) and 29-11 (0.84 g, 3 mmol) obtained above were dissolved in DMF, and potassium carbonate and 18-crown-6 were added thereto and stirred at 120 ° C. for 20 hours ( E) -4- (2- (6- (4- (2,2-diphenylvinyl) phenyl) -4,4-diphenyl-4H-silol [3,2-b: 4,5-b '] Dithiophen-2-yl) vinyl) -2-hexylthieno [3,4-b] thiophene-6-carbaldehyde was synthesized.
<3-13> 화학식 29의 화합물의 제조<3-13> Preparation of Compound of Formula 29
상기에서 얻은 화합물 29-12 (0.87g, 1 mmol)를 시아노아세트산 (0.1 g, 1.2 mmol) 및 피페리딘 (0.12 ㎖, 1.2 mmol)과 함께 아세토니트릴 (30 ㎖)에 녹인 후 4시간 동안 환류시키면서 교반하였다. 교반이 끝난 후 에틸렌클로라이드와 물을 사용하여 유기층을 추출 한 다음, 증발시키고 컬럼 정제하여 최종 염료 (E)-2-시아노-3-(4-((E)-2-(6-(4-(2,2-디페닐비닐)페닐)-4,4-디페닐-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)비닐)-2-헥실티에노[3,4-b]티오펜-6-일)아크릴산을 합성하였다.
Compound 29-12 (0.87 g, 1 mmol) obtained above was dissolved in acetonitrile (30 mL) with cyanoacetic acid (0.1 g, 1.2 mmol) and piperidine (0.12 mL, 1.2 mmol) for 4 hours. Stirring at reflux. After stirring, the organic layer was extracted with ethylene chloride and water, and then evaporated and purified by column to give the final dye (E) -2-cyano-3- (4-((E) -2- (6- (4) -(2,2-diphenylvinyl) phenyl) -4,4-diphenyl-4H-silol [3,2-b: 4,5-b '] dithiophen-2-yl) vinyl) -2-hexyl Thieno [3,4-b] thiophen-6-yl) acrylic acid was synthesized.
실시예 4: 화학식 19의 화합물의 제조Example 4: Preparation of Compound of Formula 19
[반응식 8][Reaction Scheme 8]
<4-1> 화학식 19-1의 화합물의 제조<4-1> Preparation of a compound of Formula 19-1
나트륨 (4.6 g, 200 mmol)과 촉매량의 FeCl3을 100 ㎖의 t-아밀 알콜에 녹인 후, 90℃ 에서 한 시간 동안 교반하였다. 50℃로 온도를 낮추고 티오펜-2-카보니트릴 (10.9 g, 100 mmol)을 가한 뒤 다시 온도를 90℃까지 올렸다. 디이소프로필 석시네이트 (8.09 g, 40 mmol)를 30 ㎖ t-아밀 알콜에 3시간 동안 천천히 적하한 뒤, 90℃에서 20시간 동안 교반하였다. 그 후 50℃까지 온도를 낮춘 후 40 ㎖의 빙초산을 넣고 환류온도까지 온도를 올려 바로 소결 유리 여과기로 고체를 여과하였다. 상기 고체를 가열한 메탄올과 물로 여러 번 씻은 뒤 건조하여 3,6-디(티오펜-2-일)피롤로[3,4-c]피롤-1,4(2H,5H)-디온을 합성하였다.
Sodium (4.6 g, 200 mmol) and a catalytic amount of FeCl 3 were dissolved in 100 ml of t-amyl alcohol and stirred at 90 ° C. for one hour. The temperature was lowered to 50 ° C., thiophene-2-carbonitrile (10.9 g, 100 mmol) was added, and the temperature was raised to 90 ° C. again. Diisopropyl succinate (8.09 g, 40 mmol) was slowly added dropwise to 30 ml t-amyl alcohol for 3 hours, followed by stirring at 90 ° C for 20 hours. Thereafter, after the temperature was lowered to 50 ° C., 40 ml of glacial acetic acid was added thereto, and the temperature was raised to the reflux temperature. The solid was immediately filtered through a sintered glass filter. The solid was washed several times with heated methanol and water and dried to synthesize 3,6-di (thiophen-2-yl) pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione. It was.
<4-2> 화학식 19-2의 화합물의 제조<4-2> Preparation of a compound of Formula 19-2
상기에서 얻은 화합물 19-1 (6 g, 20 mmol), K2CO3 (8.29 g,60 mmol) 및 18-크라운-6 (0.04 g)을 500 ㎖의 디메틸포름아마이드 (DMF)에 넣고 120℃까지 온도를 가하였다. 3-(브로모메틸)헵탄 (11.52 g, 60 mmol)을 30 ㎖의 DMF에 적하하고 120℃에서 6시간 동안 더 교반하였다. 그 후 상온까지 온도를 낮추고 여과하여 고체를 100 ㎖의 클로로포름과 200 ㎖의 물로 씻었다. 수득한 고체를 건조시킨 후 컬럼 정제하여 2,5-디옥틸-3,6-디(티오펜-2-일)피롤로[3,4-c]피롤-1,4(2H,5H)-디온을 합성하였다.
Compound 19-1 (6 g, 20 mmol), K 2 CO 3 (8.29 g, 60 mmol), and 18-crown-6 (0.04 g) obtained above were added to 500 mL of dimethylformamide (DMF) at 120 ° C. The temperature was added until. 3- (bromomethyl) heptane (11.52 g, 60 mmol) was added dropwise to 30 mL of DMF and further stirred at 120 ° C. for 6 hours. After cooling down to room temperature and filtered, the solid was washed with 100 ml of chloroform and 200 ml of water. The obtained solid was dried and then column purified to give 2,5-dioctyl-3,6-di (thiophen-2-yl) pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H)- Diones were synthesized.
<4-3> 화학식 19-3의 화합물의 제조<4-3> Preparation of a compound of Formula 19-3
상기에서 얻은 화합물 19-2 (5.25 g, 10 mmol)를 CCl4 (100 ㎖)에 넣고 Br2를 적하한 후 2시간 동안 상온에서 교반하였다. 그 후 디스틸하여 브롬화 반응을 마친 후, 10% NaOH로 중화하고 유기층을 분리 건조하여 3-(5-브로모티오펜-2-일)-2,5-디옥틸-6-(티오펜-2-일)피롤로[3,4-c]피롤-1,4(2H,5H)-디온을 합성하였다.
Compound 19-2 (5.25 g, 10 mmol) obtained above was added to CCl 4 (100 mL), and Br 2 was added dropwise, followed by stirring at room temperature for 2 hours. After distillation to complete the bromination reaction, the mixture was neutralized with 10% NaOH, and the organic layer was separated and dried to obtain 3- (5-bromothiophen-2-yl) -2,5-dioctyl-6- (thiophen-2). -Yl) pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione was synthesized.
<4-4> 화학식 19-4의 화합물의 제조<4-4> Preparation of a compound of Formula 19-4
4,4-디헥실-4H-실롤[3,2-b:4,5-b']디티오펜 (3.62 g, 10 mmol)을 무수 THF (150 ㎖)에 녹인 후 -78℃에서 1.6 M n-BuLi (7.5 ㎖, 12 mmol)을 서서히 적가한 후 1시간 동안 저온 교반하였다. 다시 여기에 트리부틸틴 클로라이드 (3.90 g, 12 mmol)를 -78℃에서 서서히 적가한 후 1시간 동안 저온에서 교반하고 추가로 상온에서 6시간 동안 교반하여 4,4-디헥실-2,6-비스(트리부틸스태닐)-4H-실롤[3,2-b:4,5-b']디티오펜을 합성하였다.
4,4-dihexyl-4H-silol [3,2-b: 4,5-b '] dithiophene (3.62 g, 10 mmol) was dissolved in anhydrous THF (150 mL) and 1.6 M n at -78 ° C. -BuLi (7.5 mL, 12 mmol) was added slowly dropwise and stirred at low temperature for 1 hour. Again tributyltin chloride (3.90 g, 12 mmol) was slowly added dropwise at -78 ° C and then stirred at low temperature for 1 hour and further stirred at room temperature for 6 hours to give 4,4-dihexyl-2,6- Bis (tributylstannyl) -4H-silol [3,2-b: 4,5-b '] dithiophene was synthesized.
<4-5> 화학식 19-5의 화합물의 제조<4-5> Preparation of a Compound of Formula 19-5
상기에서 얻은 화합물 19-4 (4.70 g, 5 mmol)와 N-(4-브로모페닐)-N-(9,9-디메틸-9H-플루오렌-3-일)-9,9-디메틸-9H-플루오렌-3-아민 (2.78 g, 5 mmol)을 톨루엔에 녹인 후, 스틸레 커플링 반응시키고. 반응이 끝난 후 메틸렌클로라이드와 물을 사용하여 유기층을 추출하고 증발 건조 후 컬럼 정제하여 N-(9,9-디메틸-9H-플루오렌-2-일)-N-(4-(4,4-디페닐-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)페닐)-9,9-디메틸-9H-플루오렌-2-아민을 합성하였다.
Compound 19-4 (4.70 g, 5 mmol) obtained above and N- (4-bromophenyl) -N- (9,9-dimethyl-9H-fluoren-3-yl) -9,9-dimethyl- 9H-fluorene-3-amine (2.78 g, 5 mmol) was dissolved in toluene and then subjected to Stiletto coupling reaction. After the reaction, the organic layer was extracted with methylene chloride and water, and evaporated to dryness, and then purified by column to form N- (9,9-dimethyl-9H-fluoren-2-yl) -N- (4- (4,4- Diphenyl-4H-silol [3,2-b: 4,5-b '] dithiophen-2-yl) phenyl) -9,9-dimethyl-9H-fluoren-2-amine was synthesized.
<4-6> 화학식 19-6의 화합물의 제조<4-6> Preparation of a compound of Formula 19-6
상기에서 얻은 화합물 19-5 (2.46 g, 3 mmol)에 n-BuLi (2.06 ㎖, 3.3 mmol)을 적하한 후, THF (100 ㎖)에 녹인 2-이소프로폭시-4,4,5,5-테트라메틸-1,3,2-디옥사보로란 (0.67 g, 3.6 mmol)을 넣고 100℃에서 8시간 동안 교반하여 N-(9,9-디메틸-9H-플루오렌-2-일)-N-(4-(4,4-디페닐-6-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)페닐)-9,9-디메틸-9H-플루오렌-2-아민을 합성하였다.
N-BuLi (2.06 mL, 3.3 mmol) was added dropwise to compound 19-5 (2.46 g, 3 mmol) obtained above, and then 2-isopropoxy-4,4,5,5 dissolved in THF (100 mL) was added. Add tetramethyl-1,3,2-dioxaborolane (0.67 g, 3.6 mmol) and stir at 100 ° C. for 8 hours to form N- (9,9-dimethyl-9H-fluoren-2-yl). -N- (4- (4,4-diphenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4H-silol [3 , 2-b: 4,5-b '] dithiophen-2-yl) phenyl) -9,9-dimethyl-9H-fluoren-2-amine was synthesized.
<4-7> 화학식 19-7의 화합물의 제조<4-7> Preparation of a Compound of Formula 19-7
상기에서 얻은 화합물 19-6 (1.89 g, 2 mmol)에 화합물 19-3 (1.21 g, 2 mmol)을 넣고 PTC, Aliquart 336, Pd(PPh3)4 및 Na2CO3를 THF에 적하하여 녹인 후, 디스틸 반응을 하여 3-(5-(6-(4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)-4,4-디페닐-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)티오펜-2-일)-2,5-디옥틸-6-(티오펜-2-일)피롤로[3,4-c]피롤-1,4(2H,5H)-디온을 합성하였다.
To compound 19-6 (1.89 g, 2 mmol), compound 19-3 (1.21 g, 2 mmol) was added, and PTC, Aliquart 336, Pd (PPh 3 ) 4, and Na 2 CO 3 were added dropwise to THF to dissolve it. Then, a dityl reaction was carried out to give 3- (5- (6- (4- (bis (9,9-dimethyl-9H-fluoren-2-yl) amino) phenyl) -4,4-diphenyl-4H- Silol [3,2-b: 4,5-b '] dithiophen-2-yl) thiophen-2-yl) -2,5-dioctyl-6- (thiophen-2-yl) pyrrolo [ 3,4-c] pyrrole-1,4 (2H, 5H) -dione was synthesized.
<4-8> 화학식 19-8의 화합물의 제조<4-8> Preparation of a Compound of Formula 19-8
1,2-디클로로에탄 (30 ㎖)에 상기에서 얻은 화합물 19-7 (5.42 g, 4.03 mmol)과 DMF (0.35 g, 4.84 mmol)를 함께 넣고 교반시킨 뒤, 저온 (0℃)에서 포스포러스 클로라이드 옥사이드 (0.74 g, 4.84 mmol)를 적가하고 80℃에서 4시간 동안 반응시켜 5-(4-(5-(6-(4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)-4,4-디페닐-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)티오펜-2-일)-2,5-디옥틸-3,6-디옥소-2,3,5,6-테트라하이드로피롤로[3,4-c]피롤-1-일)티오펜-2-카브알데하이드를 합성하였다.
To compound 1,2-7 (5.42 g, 4.03 mmol) and DMF (0.35 g, 4.84 mmol) obtained above were mixed in 1,2-dichloroethane (30 mL), followed by stirring at low temperature (0 ° C.). Oxide (0.74 g, 4.84 mmol) was added dropwise and reacted at 80 ° C. for 4 hours to give 5- (4- (5- (6- (4- (bis (9,9-dimethyl-9H-fluoren-2-yl) ) Amino) phenyl) -4,4-diphenyl-4H-silol [3,2-b: 4,5-b '] dithiophen-2-yl) thiophen-2-yl) -2,5-di Octyl-3,6-dioxo-2,3,5,6-tetrahydropyrrolo [3,4-c] pyrrol-1-yl) thiophene-2-carbaldehyde was synthesized.
<4-9> 화학식 19의 화합물의 제조<4-9> Preparation of Compound of Formula 19
상기에서 얻은 화합물 19-8 (2.74 g, 2 mmol)을 시아노아세트산 (0.2 g, 2.4 mmol) 및 피페리딘 (0.24 ㎖, 2.4 mmol)과 함께 아세토니트릴 (50 ㎖)에 녹인 후 4시간 동안 환류시키면서 교반하였다. 교반이 끝난 후 에틸렌클로라이드와 물을 사용하여 유기층을 추출 후 증발을 한 뒤 컬럼 정제하여 최종 염료 (E)-3-(5-(4-(5-(6-(4-(비스(9,9-디메틸-9H-플루오렌-2-일)아미노)페닐)-4,4-디페닐-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)티오펜-2-일)-2,5-디옥틸-3,6-디옥소-2,3,5,6-테트라하이드로피롤로[3,4-c]피롤-1-일)티오펜-2-일)-2-시아노아크릴산을 합성하였다.
Compound 19-8 (2.74 g, 2 mmol) obtained above was dissolved in acetonitrile (50 mL) with cyanoacetic acid (0.2 g, 2.4 mmol) and piperidine (0.24 mL, 2.4 mmol) for 4 hours. Stirring at reflux. After stirring, the organic layer was extracted using ethylene chloride and water, evaporated, and then purified by column to obtain final dye (E) -3- (5- (4- (5- (6- (4- (bis (9, 9-dimethyl-9H-fluoren-2-yl) amino) phenyl) -4,4-diphenyl-4H-silol [3,2-b: 4,5-b '] dithiophen-2-yl) thi Offen-2-yl) -2,5-dioctyl-3,6-dioxo-2,3,5,6-tetrahydropyrrolo [3,4-c] pyrrol-1-yl) thiophen-2 -Yl) -2-cyanoacrylic acid was synthesized.
실시예 5: 화학식 20의 화합물의 제조Example 5: Preparation of Compound of Formula 20
[반응식 9]Scheme 9
<5-1> 화학식 20-1의 화합물의 제조<5-1> Preparation of a compound of formula 20-1
상기 실시예 <3-1>과 동일한 방법으로 디에틸 4-브로모벤질포스포네이트를 합성하였다.
Diethyl 4-bromobenzylphosphonate was synthesized in the same manner as in Example <3-1>.
<5-2> 화학식 20-2의 화합물의 제조<5-2> Preparation of a compound of formula 20-2
상기 실시예 <3-2>와 동일한 방법으로 (2-(4-브로모페닐)에텐-1,1-디일)디벤젠을 합성하였다.
(2- (4-bromophenyl) ethene-1,1-diyl) dibenzene was synthesized in the same manner as in Example <3-2>.
<5-3> 화학식 20-3의 화합물의 제조<5-3> Preparation of a compound of Formula 20-3
상기에서 얻은 화합물 20-2 (5.02 g ,15 mmol)를 무수 THF (50 ㎖)에 녹인 후 -78℃에서 1.6 M n-BuLi(11.25 ㎖, 18 mmol)을 서서히 적가하고 1시간 동안 저온 교반하였다. 다시 여기에 트리부틸틴 클로라이드 (6.10 g, 18 mmol)를 -78℃에서 서서히 적가한 후 1시간 동안 저온에서 교반하고 추가로 상온에서 6시간 동안 교반하여 트리부틸(4-(2,2-디페닐비닐)페닐)스태난을 합성하였다.
Compound 20-2 (5.02 g, 15 mmol) obtained above was dissolved in anhydrous THF (50 mL), and 1.6 M n-BuLi (11.25 mL, 18 mmol) was slowly added dropwise at -78 ° C and stirred for 1 hour at low temperature. . Again tributyltin chloride (6.10 g, 18 mmol) was slowly added dropwise at -78 ℃ and stirred for 1 hour at low temperature and further stirred at room temperature for 6 hours to give tributyl (4- (2,2-di Phenylvinyl) phenyl) stanan was synthesized.
<5-4> 화학식 20-4의 화합물의 제조<5-4> Preparation of a compound of formula 20-4
(2,4,4,6-테트라메틸-4H-실롤[3,2-b:4,5-b']디티오펜 (7.50 g, 30 mmol)을 DMF (100 ㎖)에 녹인 후, NBS (6.39 g, 36 mmol)를 저온 (0℃)에서 적하하고 실온에서 4시간 동안 반응시켜 2-브로모-4,4,6-트리메틸-4H-실롤[3,2-b:4,5-b']디티오펜를 합성하였다.
(2,4,4,6-tetramethyl-4H-silol [3,2-b: 4,5-b '] dithiophene (7.50 g, 30 mmol) was dissolved in DMF (100 mL), followed by NBS ( 6.39 g, 36 mmol) was added dropwise at low temperature (0 ° C) and reacted at room temperature for 4 hours to give 2-bromo-4,4,6-trimethyl-4H-silol [3,2-b: 4,5-b '] Dithiophene was synthesized.
<5-5> 화학식 20-5의 화합물의 제조<5-5> Preparation of a Compound of Formula 20-5
상기에서 얻은 화합물 20-4 (4.70 g, 15 mmol) 및 2-(2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)-4,4,5,5-테트라메틸-1,3,2-디옥사보로란 (4.82 g, 18 mmol)을 Pd(PPh3)4 (1.04 g, 0.9 mmol) 및 포타슘 카보네이트 (2.07 g, 45 mmol)에 넣고 THF (150 ㎖)에 녹인 후 질소 가스 상태하에서 12시간 동안 환류시키면서 교반하였다. 교반이 끝난 후 메틸렌클로라이드와 물을 사용하여 유기층을 추출하고 증발을 통하여 건조 후 컬럼 정제하여 2-(2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)-4,4,6-트리메틸-4H-실롤[3,2-b:4,5-b']디티오펜을 합성하였다.
Compounds 20-4 (4.70 g, 15 mmol) and 2- (2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) -4,4, obtained above 5,5-tetramethyl-1,3,2-dioxaborolane (4.82 g, 18 mmol) was added to Pd (PPh 3 ) 4 (1.04 g, 0.9 mmol) and potassium carbonate (2.07 g, 45 mmol). It was dissolved in THF (150 mL) and stirred under reflux for 12 hours under nitrogen gas. After stirring, the organic layer was extracted using methylene chloride and water, dried by evaporation, and then purified by column to obtain 2- (2,3-dihydrothieno [3,4-b] [1,4] dioxine-5. -Yl) -4,4,6-trimethyl-4H-silol [3,2-b: 4,5-b '] dithiophene was synthesized.
<5-6> 화학식 20-6의 화합물의 제조<5-6> Preparation of a compound of formula 20-6
상기에서 얻은 화합물 20-5 (3.76 g, 10 mmol)와 NBS (2.13 g, 12 mmol)를 THF (100 ㎖)에 녹인 후 상온에서 4시간 동안 질소가스 상태 하에서 교반하였다. 그 다음, 메틸렌클로라이드와 물을 사용하여 유기층을 추출하고 증발시킨 뒤 컬럼 정제하여 2-(7-브로모-2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)-4,4,6-트리메틸-4H-실롤[3,2-b:4,5-b']디티오펜을 합성하였다.
Compound 20-5 (3.76 g, 10 mmol) and NBS (2.13 g, 12 mmol) obtained above were dissolved in THF (100 mL) and stirred under nitrogen gas at room temperature for 4 hours. Then, the organic layer was extracted with methylene chloride and water, evaporated and purified by column to give 2- (7-bromo-2,3-dihydrothieno [3,4-b] [1,4] dioxine. -5-yl) -4,4,6-trimethyl-4H-silol [3,2-b: 4,5-b '] dithiophene was synthesized.
<5-7> 화학식 20-7의 화합물의 제조<5-7> Preparation of the compound of formula 20-7
상기에서 얻은 화합물 20-6 (3.18 g, 7 mmol)과 20-3 (3.81 g, 7 mmol)을 톨루엔에 녹인 후, 스틸레 커플링 반응시켰다. 반응이 끝난 후 메틸렌클로라이드와 물을 사용하여 유기층을 추출 후 증발건조하고 컬럼 정제하여 2-(7-(4-(2,2-디페닐비닐)페닐)-2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)-4,4,6-트리메틸-4H-실롤[3,2-b:4,5-b']디티오펜을 합성하였다.
Compound 20-6 (3.18 g, 7 mmol) and 20-3 (3.81 g, 7 mmol) obtained above were dissolved in toluene and then subjected to a stille coupling reaction. After completion of the reaction, the organic layer was extracted using methylene chloride and water, evaporated to dryness and column purified to obtain 2- (7- (4- (2,2-diphenylvinyl) phenyl) -2,3-dihydrothieno [ 3,4-b] [1,4] dioxin-5-yl) -4,4,6-trimethyl-4H-silol [3,2-b: 4,5-b '] dithiophene was synthesized.
<5-8> 화학식 20-8의 화합물의 제조<5-8> Preparation of a Compound of Formula 20-8
상기에서 얻은 화합물 20-7 (3.15 g, 5 mmol)을 DMF (30 ㎖)에 녹인 후 NBS (1.06 g, 6 mmol)를 저온 (0℃)에서 적하하고 실온에서 4시간 동안 반응시켜 2-브로모-6-(7-(4-(2,2-디페닐비닐)페닐)-2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)-4,4-디메틸-4H-실롤[3,2-b:4,5-b']디티오펜을 합성하였다.
Compound 20-7 (3.15 g, 5 mmol) obtained above was dissolved in DMF (30 mL), NBS (1.06 g, 6 mmol) was added dropwise at low temperature (0 ° C), and reacted at room temperature for 4 hours. Mo-6- (7- (4- (2,2-diphenylvinyl) phenyl) -2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl)- 4,4-dimethyl-4H-silol [3,2-b: 4,5-b '] dithiophene was synthesized.
<5-9> 화학식 20-9의 화합물의 제조<5-9> Preparation of a compound of formula 20-9
상기에서 얻은 화합물 20-8 (2.08 g, 3 mmol)에 (E)-((5-옥소티에노[3,2-b]티오펜-2(5H)-일리덴)메틸)보론산 (0.63 g, 3 mmol), Pd(PPh3)4 (0.17 g, 0.15 mmol) 및 포타슘 카보네이트 (1.24 g, 9 mmol)를 넣고 DMF (100 ㎖)에 녹인 후 질소가스 상태 하에서 12시간 동안 환류시켜 교반하였다. 교반이 끝난 후 메틸렌클로라이드와 물을 사용하여 유기층을 추출하고 증발시킨 뒤 컬럼정제하여 (E)-5-((6-(7-(4-(2,2-디페닐비닐)페닐)-2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)-4,4-디메틸-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)메틸렌)티에노[3,2-b]티오펜-2(5H)-온을 합성하였다.
To compound 20-8 (2.08 g, 3 mmol) obtained above (E)-((5-oxothieno [3,2-b] thiophene-2 (5H) -ylidene) methyl) boronic acid (0.63 g, 3 mmol), Pd (PPh 3 ) 4 (0.17 g, 0.15 mmol) and potassium carbonate (1.24 g, 9 mmol) were added and dissolved in DMF (100 mL), and the mixture was refluxed under nitrogen gas for 12 hours and stirred. . After stirring, the organic layer was extracted using methylene chloride and water, evaporated and purified by column (E) -5-((6- (7- (4- (2,2-diphenylvinyl) phenyl) -2 , 3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) -4,4-dimethyl-4H-silol [3,2-b: 4,5-b '] Dithiophen-2-yl) methylene) thieno [3,2-b] thiophen-2 (5H) -one was synthesized.
<5-10> 화학식 20의 화합물의 제조<5-10> Preparation of a Compound of Formula 20
상기에서 얻은 화합물 20-9 (1.09 g, 1.4 mmol), 시아노아세트산 (0.14 g, 1.68 mmol) 및 피페리딘 (0.36 ㎖, 3.7 mmol)을 아세토니트릴 (30 ㎖)에 녹인 후 4시간 동안 환류시키면서 교반하였다. 교반이 끝난 후 메틸렌클로라이드와 물을 사용하여 유기층을 추출 후 증발 건조하여 컬럼 정제하여 최종 염료 (E)-2-시아노-2-((E)-5-((6-(7-(4-(2,2-디페닐비닐)페닐)-2,3-디하이드로티에노[3,4-b][1,4]디옥신-5-일)-4,4-디메틸-4H-실롤[3,2-b:4,5-b']디티오펜-2-일)메틸렌)티에노[3,2-b]티오펜-2(5H)-일리덴)아세트산을 합성하였다.Compound 20-9 (1.09 g, 1.4 mmol), cyanoacetic acid (0.14 g, 1.68 mmol) and piperidine (0.36 mL, 3.7 mmol) obtained above were dissolved in acetonitrile (30 mL) and then refluxed for 4 hours. Stirring while stirring. After stirring, the organic layer was extracted using methylene chloride and water, and then evaporated to dryness. -(2,2-diphenylvinyl) phenyl) -2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl) -4,4-dimethyl-4H-silol [3,2-b: 4,5-b '] dithiophen-2-yl) methylene) thieno [3,2-b] thiophene-2 (5H) -ylidene) acetic acid was synthesized.
실시예 6: 화학식 23의 화합물의 제조Example 6: Preparation of Compound of Formula 23
[반응식 10][Reaction Scheme 10]
<6-1> 화학식 23의 화합물의 제조<6-1> Preparation of Compound of Formula 23
135℃ 온도 조건 하에서 디메틸(5-메틸-2-(6-메틸나프탈린-2-일)페닐)실란 (4.35 g, 15 mmol), RhCl(PPh3)3 (0.58 mg,0.075 mmol) 및 1,4-디옥산 (15 ㎖)을 밀폐된 반응기 안에서 15분 동안 교반시킨 후, 상기 합성방법에 따라 합성 및 정제를 하였다. 기타 구체적인 합성 및 정제방법은 상기 실시예 2의 화합물 21의 합성방법과 정제방법을 준용하였다.
Dimethyl (5-methyl-2- (6-methylnaphthalin-2-yl) phenyl) silane (4.35 g, 15 mmol), RhCl (PPh 3 ) 3 (0.58 mg, 0.075 mmol) and 1 under 135 ° C. temperature conditions , 4-Dioxane (15 mL) was stirred in a closed reactor for 15 minutes, and then synthesized and purified according to the above synthesis method. For other specific synthesis and purification methods, the synthesis method and purification method of Compound 21 of Example 2 were applied mutatis mutandis.
실시예 7: 화학식 30의 화합물의 제조Example 7: Preparation of Compound of Formula 30
[반응식 11][Reaction Scheme 11]
<7-1> 화학식 30의 화합물의 제조<7-1> Preparation of Compound of Formula 30
135℃ 온도 조건 하에서 디메틸(5-메틸-2-(5-메틸티오핀-3-일)페닐)실란 (3.70 g, 15 mmol), RhCl(PPh3)3 (0.58 mg,0.075 mmol) 및 1,4-디옥산 (15 ㎖)을 밀폐된 반응기 안에서 15분 동안 교반시킨 후, 상기 합성방법에 따라 합성 및 정제를 하였다. 기타 구체적인 합성 및 정제방법은 상기 실시예 2의 화합물 21의 합성방법과 정제방법을 준용하였다.
Dimethyl (5-methyl-2- (5-methylthiopin-3-yl) phenyl) silane (3.70 g, 15 mmol), RhCl (PPh 3 ) 3 (0.58 mg, 0.075 mmol) and 1 under 135 ° C. temperature conditions , 4-Dioxane (15 mL) was stirred in a closed reactor for 15 minutes, and then synthesized and purified according to the above synthesis method. For other specific synthesis and purification methods, the synthesis method and purification method of Compound 21 of Example 2 were applied mutatis mutandis.
실시예 8: 화학식 22의 화합물의 제조Example 8: Preparation of Compound of Formula 22
[반응식 12] [Reaction Scheme 12]
<8-1> 화학식 22의 화합물의 제조<8-1> Preparation of Compound of Formula 22
135℃ 온도 조건 하에서 (5,5''-디메틸-[1,1':4',1''-터페닐]-2,2''-디일)비스(디메칠실란)(5.62 g, 15 mmol), RhCl(PPh3)3 (0.58 mg,0.075 mmol) 및 1,4-디옥산 (15 ㎖)을 밀폐된 반응기 안에서 15분 동안 교반시킨 후, 상기 합성방법에 따라 합성 및 정제를 하였다. 기타 구체적인 합성 및 정제방법은 상기 실시예 2의 화합물 21의 합성방법과 정제방법을 준용하였다.
(5,5 ''-Dimethyl- [1,1 ': 4', 1 ''-terphenyl] -2,2 ''-diyl) bis (dimethylsilane) (5.62 g, 15 mmol), RhCl (PPh 3 ) 3 (0.58 mg, 0.075 mmol) and 1,4-dioxane (15 mL) were stirred in a closed reactor for 15 minutes, and then synthesized and purified according to the above synthesis method. For other specific synthesis and purification methods, the synthesis method and purification method of Compound 21 of Example 2 were applied mutatis mutandis.
실시예 9 : 염료감응태양전지의 제조 및 물성 측정Example 9 Preparation and Measurement of Dye-Sensitized Solar Cell
염료 화합물의 전류-전압 특성을 평가하기 위해, 8 ㎛ TiO2 투명층을 이용하여 태양전지를 제조하였다. TiO2 페이스트(Solaronix, 13nm 페이스트)를 스크린 프린팅하여 8 ㎛ 두께의 TiO2 투명층을 제조하였다. 이 TiO2 필름을 40mM TiCl4 용액으로 처리하고 500℃에서 30분간 건조하였다. 처리된 필름을 60℃로 냉각한 후, 상기 실시예 1부터 8까지에서 제조된 본 발명의 염료 화합물 19, 20, 22, 23, 28, 29, 30 각각의 용액(10mM의 케노디옥시콜산 함유 디메틸포름아미드와 에탄올의 혼합물(2ml:8ml) 중에 0.3mM 염료)에 함침시켰다. 참조(Reference)로서 N719의 에탄올 용액을 사용하였다. 염료-흡착된 TiO2 전극과 백금-대전극 사이에 스페이서로서 고온용융 필름(Surlyn 1702, 25㎛ 두께)을 놓고 가열하여 밀봉된 샌드위치 전지를 조합하였다. 전해질 용액으로는 아세토니트릴 중에 0.6 M 3-헥실-1,2-디메틸이미다졸리움 요오드, 0.04 M I2, 0.025 M LiI 및 0.28 M tert-부틸피리딘을 용해시킨 것을 사용하였다.In order to evaluate the current-voltage characteristics of the dye compound, a solar cell was manufactured using an 8 μm TiO 2 transparent layer. A TiO 2 paste (Solaronix, 13 nm paste) was screen printed to produce an 8 μm thick TiO 2 transparent layer. This TiO 2 film was treated with 40 mM TiCl 4 solution and dried at 500 ° C. for 30 minutes. After cooling the treated film to 60 ℃, each of the dye compounds 19, 20, 22, 23, 28, 29, 30 of the present invention prepared in Examples 1 to 8 (containing 10 mM Kenodioxycholic acid Impregnated with 0.3 mM dye in a mixture of dimethylformamide and ethanol (2 ml: 8 ml). As a reference, an ethanol solution of N719 was used. A sealed sandwich cell was assembled by heating a hot melt film (Surlyn 1702, 25 μm thick) as a spacer between the dye-adsorbed TiO 2 electrode and the platinum-electrode. As the electrolyte solution, a solution of 0.6 M 3-hexyl-1,2-dimethylimidazolium iodine, 0.04 MI 2 , 0.025 M LiI and 0.28 M tert -butylpyridine in acetonitrile was used.
참조 화합물로서 사용된 N719는 종래 염료감응태양전지에 사용되는 루테늄계 촉매로 하기와 같은 구조를 갖는다.N719 used as a reference compound is a ruthenium-based catalyst used in conventional dye-sensitized solar cells and has a structure as follows.
상기 제조된 태양전지의 광전자화학특성(photoelectrochemical characteristics)을 측정하여 하기 표 1에 나타내었다. 태양전지의 광전자화학특성은 Keithley M 236 소스 측정 장치를 이용하여 측정하였으며, 광원으로는 AM 1.5 필터(Oriel)가 구비된 300 W Xe 램프를 이용하였고, 전극크기는 0.4 ×0.4 cm2, 빛의 세기는 1 sun(100 mW/cm2)으로 하였다. 빛의 세기는 Si 태양전지를 이용하여 조정하였다.
The photoelectrochemical characteristics of the manufactured solar cell are measured and shown in Table 1 below. The photoelectrochemical characteristics of the solar cell were measured using a Keithley M 236 source measuring device, and a 300 W Xe lamp equipped with an AM 1.5 filter (Oriel) was used as the light source, and the electrode size was 0.4 × 0.4 cm 2 . The intensity was 1 sun (100 mW / cm 2 ). Light intensity was adjusted using a Si solar cell.
상기 표 1의 결과로부터 알 수 있는 바와 같이 본 발명의 신규 염료는 우수한 몰흡광계수, Jsc(단회로 광전류 밀도) 및 광전기 변환효율을 나타냄을 확인 할 수 있다. 상기 표 1에서, Jsc는 단회로 광전류 밀도(short-circuit photocurrent density), Voc는 오픈 회로 광전압(open circuit photovoltage), FF는 충전 인자(fill factor)를 나타낸다.As can be seen from the results of Table 1, it can be seen that the novel dye of the present invention exhibits excellent molar absorption coefficient, Jsc (short circuit photocurrent density) and photoelectric conversion efficiency. In Table 1, J sc represents a short-circuit photocurrent density, V oc represents an open circuit photovoltage, and FF represents a fill factor.
Claims (8)
DO - Qm - B - Qn - AC
상기 화학식 1에서,
B는
Q는
DO는 지방족 화합물을 포함하는 전자 주개 그룹으로서, C1-50의 알킬, 이소알킬(가지형 알킬), 아릴, 알콕시, 알켄, 알킨, 실록시, 아민, 할로겐, 시아노, 하이드록실, 니트로, 아실, 아릴 또는 헤테로아릴기로 치환되거나 치환되지 않은 C1-50의 알킬, 아릴, 알콕시 또는 헤테로아릴이며;
AC는 시아노아크릴산기를 포함하는 전자 받개 그룹으로서, 하나 이상의 할로겐, C1-10 알킬, 또는 모노, 디 또는 트리페닐메틸로 치환되거나 치환되지 않은 시아노아크릴산기이고;
R1, R2, R3, R4, Y 및 Z는 각각 독립적으로 수소, 또는 헤테로 원자 또는 치환기로 치환되거나 치환되지 않은 1 내지 50의 탄소 수를 가지는 알킬, 이소알킬 (가지형 알킬), 아릴, 알콕시, 헤테로아릴, 알켄, 알킨, 실록시, 시아노, 하이드록실, 니트로, 아민, 아실, 시클로알켄 또는 시클로알킨이고;
A, X1 및 X2는 각각 독립적으로 C, O, S, Si, Ge, Sn, Pb 또는Se, Te 이고;
m 및 n은 각각 독립적으로 0 내지 10의 정수이다.[Formula 1]
DO-Qm-B-Qn-AC
In Chemical Formula 1,
B is
Q is
DO is an electron donor group containing an aliphatic compound, which is C 1-50 alkyl, isoalkyl (branched alkyl), aryl, alkoxy, alkene, alkyne, siloxy, amine, halogen, cyano, hydroxyl, nitro, C 1-50 alkyl, aryl, alkoxy or heteroaryl unsubstituted or substituted with an acyl, aryl or heteroaryl group;
AC is an electron acceptor group comprising a cyanoacrylic acid group, which is a cyanoacrylic acid group which is optionally substituted with one or more halogens, C 1-10 alkyl, or mono, di or triphenylmethyl;
R 1 , R 2 , R 3 , R 4 , Y and Z are each independently hydrogen or alkyl having 1 to 50 carbon atoms, unsubstituted or substituted with a hetero atom or a substituent, isoalkyl (branched alkyl), Aryl, alkoxy, heteroaryl, alkene, alkyne, siloxy, cyano, hydroxyl, nitro, amine, acyl, cycloalkene or cycloalkyne;
A, X 1 and X 2 are each independently C, O, S, Si, Ge, Sn, Pb or Se, Te;
m and n are each independently an integer of 0-10.
상기 전자 주개 그룹 (DO)이 하기 구조식들로 이루어진 군으로부터 선택되는 것을 특징으로 하는 유기염료:
상기에서,
*는 결합부분이고;
R5, R6 및 R7은 각각 독립적으로 수소, 헤테로원자 또는 치환기로 치환되거나 치환되지 않은 1 내지 50의 탄소 수를 가지는 알킬, 이소알킬, 아릴, 알콕시, 헤테로아릴, 알켄, 알킨, 아민, 할로겐, 시아노, 하이드록실, 니트로, 아실, 실록시, 시클로알켄, 시클로알킨 또는 시클로헤테로알켄이다.The method of claim 1,
Wherein said electron donor group (DO) is selected from the group consisting of the following structural formulas:
In the above,
* Is a binding moiety;
R 5 , R 6 and R 7 are each independently alkyl, isoalkyl, aryl, alkoxy, heteroaryl, alkene, alkyne, amine, having 1 to 50 carbon atoms, unsubstituted or substituted with hydrogen, heteroatoms or substituents; Halogen, cyano, hydroxyl, nitro, acyl, siloxy, cycloalkene, cycloalkyne or cycloheteroalkene.
상기 전자 받개 그룹 (AC)가 하기 구조식들로 이루어진 군으로부터 선택되는 것을 특징으로 하는 유기염료:
상기에서,
W 및 Z는 각각 독립적으로 수소, 헤테로원자 또는 치환기로 치환되거나 치환되지 않은 1 내지 50의 탄소 수를 가지는 알킬, 이소알킬, 아릴, 알콕시, 헤테로아릴, 알켄, 알킨, 실록시, 시아노, 하이드록실, 니트로, 아실, 아민, 시클로알켄, 시클로알킨 또는 시클로헤테로알켄이고;
p 및 q는 각각 독립적으로 0 내지 10의 정수이며;
S는 O, S, Se 또는 Te 이다.The method of claim 1,
The organic acceptor group (AC) is selected from the group consisting of the following structural formulas:
In the above,
W and Z each independently represent an alkyl, isoalkyl, aryl, alkoxy, heteroaryl, alkene, alkyne, siloxy, cyano, hydroxy having from 1 to 50 carbon atoms, unsubstituted or substituted with a hydrogen, heteroatom or substituent Hydroxyl, nitro, acyl, amine, cycloalkene, cycloalkyne or cycloheteroalkene;
p and q are each independently integers of 0 to 10;
S is O, S, Se or Te.
상기 DO와 Qm 사이, Qm과 B사이, B와 Qn사이, 또는 Qn과 AC 사이에 하기와 같은 구조식을 갖는 화합물(S1)을 추가로 포함하는 것을 특징으로 하는 유기염료:
또는 이들의 조합.
상기에서,
R8, R9 및 R10은 각각 독립적으로 수소, 헤테로원자 또는 치환기로 치환되거나 치환되지 않은 1 내지 50의 탄소 수를 가지는 알킬, 이소알킬, 아릴, 알콕시, 헤테로아릴, 알켄, 알킨, 아민, 실록시, 시아노, 하이드록실, 니트로, 아실, 아민, 시클로알켄, 시클로알킨 또는 시클로헤테로알켄이고;
X3 및 X4는 각각 독립적으로 O, S, Se 또는 Te 이며;
k는 0 내지 10의 정수이다.The method of claim 1,
An organic dye further comprising a compound (S1) having the following structural formula between the DO and Qm, between Qm and B, between B and Qn, or between Qn and AC:
Or combinations thereof.
In the above,
R 8 , R 9 and R 10 are each independently alkyl, isoalkyl, aryl, alkoxy, heteroaryl, alkene, alkyne, amine, having 1 to 50 carbon atoms, unsubstituted or substituted with hydrogen, heteroatoms or substituents; Siloxy, cyano, hydroxyl, nitro, acyl, amine, cycloalkene, cycloalkyne or cycloheteroalkene;
X 3 and X 4 are each independently O, S, Se or Te;
k is an integer of 0-10.
상기 화학식 1의 염료가 하기 화학식 8 내지 32 중 어느 하나로 표시되는 화합물인 것을 특징으로 하는 유기염료:
[화학식 8]
[화학식 9]
[화학식 10]
[화학식 11]
[화학식 12]
[화학식 13]
[화학식 14]
[화학식 15]
[화학식 16]
[화학식 17]
[화학식 18]
[화학식 19]
[화학식 20]
[화학식 21]
[화학식 22]
[화학식 23]
[화학식 24]
[화학식 25]
[화학식 26]
[화학식 27]
[화학식 28]
[화학식 29]
[화합물 30]
[화학식 31]
[화학식 32]
An organic dye, characterized in that the dye of Formula 1 is a compound represented by any one of the following Formulas 8 to 32:
[Chemical Formula 8]
[Chemical Formula 9]
[Formula 10]
(11)
[Chemical Formula 12]
[Chemical Formula 13]
[Chemical Formula 14]
[Chemical Formula 15]
[Chemical Formula 16]
[Chemical Formula 17]
[Chemical Formula 18]
[Chemical Formula 19]
[Chemical Formula 20]
[Chemical Formula 21]
[Chemical Formula 22]
(23)
[Formula 24]
[Formula 25]
[Formula 26]
[Formula 27]
[Formula 28]
[Formula 29]
[Compound 30]
(31)
(32)
(2) 유기용매에 녹인 전자 받개 화합물과 상기 단계 (1)에서 얻어진 화합물을 반응시키는 단계를 포함하는, 청구항 1의 화학식 1로 표시되는 염료의 제조방법.(1) dissolving a compound comprising a spacer moiety in an organic solvent, and then reacting with n-butyllithium at low temperature, followed by reaction with an electron donor compound substituted with halogen at the same temperature; And
(2) A method for producing a dye represented by the formula (1) comprising the step of reacting the electron acceptor compound dissolved in the organic solvent and the compound obtained in the step (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120042542A KR20120120906A (en) | 2011-04-25 | 2012-04-24 | Novel organic dye and preparation thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110038355 | 2011-04-25 | ||
| KR1020120042542A KR20120120906A (en) | 2011-04-25 | 2012-04-24 | Novel organic dye and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20120120906A true KR20120120906A (en) | 2012-11-02 |
Family
ID=47507493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020120042542A KR20120120906A (en) | 2011-04-25 | 2012-04-24 | Novel organic dye and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20120120906A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113755024A (en) * | 2021-09-14 | 2021-12-07 | 河南科技大学 | Pure organic photosensitive dye with stepped energy transfer structure and preparation method and application thereof |
| US11299466B2 (en) | 2016-04-12 | 2022-04-12 | Lg Chem, Ltd. | Compound, and organic electronic element comprising same |
-
2012
- 2012-04-24 KR KR1020120042542A patent/KR20120120906A/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11299466B2 (en) | 2016-04-12 | 2022-04-12 | Lg Chem, Ltd. | Compound, and organic electronic element comprising same |
| CN113755024A (en) * | 2021-09-14 | 2021-12-07 | 河南科技大学 | Pure organic photosensitive dye with stepped energy transfer structure and preparation method and application thereof |
| CN113755024B (en) * | 2021-09-14 | 2023-05-26 | 河南科技大学 | Pure organic photosensitive dye with stepped energy transfer structure, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pei et al. | Dye-sensitized solar cells based on quinoxaline dyes: effect of π-linker on absorption, energy levels, and photovoltaic performances | |
| Wang et al. | Organic dyes containing dithieno [2, 3-d: 2′, 3′-d′] thieno [3, 2-b: 3′, 2′-b′] dipyrrole core for efficient dye-sensitized solar cells | |
| Huang et al. | Novel D–A–π–A organic dyes based on 3-dimensional triarylamine and benzothiadiazole derivatives for high-performance dye-sensitized solar cells | |
| Cheng et al. | Organic dyes incorporating the cyclopentadithiophene moiety for efficient dye-sensitized solar cells | |
| Zhou et al. | Multi-alkylthienyl appended porphyrins for efficient dye-sensitized solar cells | |
| Zhou et al. | Porphyrins modified with a low-band-gap chromophore for dye-sensitized solar cells | |
| Shi et al. | New sensitizers bearing quinoxaline moieties as an auxiliary acceptor for dye-sensitized solar cells | |
| Liu et al. | The enhancement of photovoltaic properties of the DSSCs based on D–A–π–A organic dyes via tuning auxiliary acceptor | |
| KR101982944B1 (en) | Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye solution, and terpyridine compound or esterification product thereof | |
| Cai et al. | Molecular engineering of the fused azacycle donors in the DA-π-A metal-free organic dyes for efficient dye-sensitized solar cells | |
| Keerthi et al. | Architectural influence of carbazole push–pull–pull dyes on dye sensitized solar cells | |
| Lu et al. | Novel D–π–A porphyrin dyes with different alkoxy chains for use in dye-sensitized solar cells | |
| Massin et al. | Molecular engineering of carbazole-fluorene sensitizers for high open-circuit voltage DSSCs: Synthesis and performance comparison with iodine and cobalt electrolytes | |
| Prakash et al. | Facile synthesis of β-functionalized “push-pull” Zn (II) porphyrins for DSSC applications | |
| Ma et al. | Impact of π-conjugation configurations on the photovoltaic performance of the quinoxaline-based organic dyes | |
| Liu et al. | Influence of the auxiliary acceptor and π-bridge in carbazole dyes on photovoltaic properties | |
| Han et al. | Phenothiazine dyes containing a 4-phenyl-2-(thiophen-2-yl) thiazole bridge for dye-sensitized solar cells | |
| Jia et al. | New D–π–A dyes incorporating dithieno [3, 2-b: 2′, 3′-d] pyrrole (DTP)-based π-spacers for efficient dye-sensitized solar cells | |
| Arrechea et al. | Charge recombination losses in thiophene-substituted porphyrin dye-sensitized solar cells | |
| KR101808982B1 (en) | Photoelectric conversion element, dye-sensitized solar cell, metal-complex pigment, pigment solution, and terpyridine compound or esterified terpyridine compound | |
| WO2013008951A1 (en) | Organic dye, dye-sensitized metal oxide semiconductor electrode and dye-sensitized solar cell | |
| KR101947886B1 (en) | Photoelectric conversion element, dye-sensitized solar cell, metal-complex pigment, and pigment solution | |
| Cheng et al. | Dithiafulvene-based organic sensitizers using pyridine as the acceptor for dye-sensitized solar cells | |
| KR20120120906A (en) | Novel organic dye and preparation thereof | |
| KR20140082569A (en) | Novel organic dye and method for preparing thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WITN | Application deemed withdrawn, e.g. because no request for examination was filed or no examination fee was paid |