KR101218318B1 - NOBLE Ru-TYPE PHOTOSENSITIZER FOR PHOTOVOLTAIC CELL AND PHOTOVOLTAIC CELL PREPARED FROM THE SAME - Google Patents
NOBLE Ru-TYPE PHOTOSENSITIZER FOR PHOTOVOLTAIC CELL AND PHOTOVOLTAIC CELL PREPARED FROM THE SAME Download PDFInfo
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- KR101218318B1 KR101218318B1 KR1020100067553A KR20100067553A KR101218318B1 KR 101218318 B1 KR101218318 B1 KR 101218318B1 KR 1020100067553 A KR1020100067553 A KR 1020100067553A KR 20100067553 A KR20100067553 A KR 20100067553A KR 101218318 B1 KR101218318 B1 KR 101218318B1
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- 239000003504 photosensitizing agent Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 284
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 8
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 7
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 7
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 6
- 125000001769 aryl amino group Chemical group 0.000 claims abstract description 6
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 6
- 125000004986 diarylamino group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 30
- -1 pentarenyl group Chemical group 0.000 claims description 20
- 239000004065 semiconductor Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- 239000010419 fine particle Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 230000031700 light absorption Effects 0.000 claims description 3
- 125000004627 thianthrenyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3SC12)* 0.000 claims description 3
- OGNSDRMLWYNUED-UHFFFAOYSA-N 1-cyclohexyl-4-[4-[4-(4-cyclohexylcyclohexyl)cyclohexyl]cyclohexyl]cyclohexane Chemical group C1CCCCC1C1CCC(C2CCC(CC2)C2CCC(CC2)C2CCC(CC2)C2CCCCC2)CC1 OGNSDRMLWYNUED-UHFFFAOYSA-N 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000005509 dibenzothiophenyl group Chemical group 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000002636 imidazolinyl group Chemical group 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000001041 indolyl group Chemical group 0.000 claims description 2
- 125000002757 morpholinyl group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000002971 oxazolyl group Chemical group 0.000 claims description 2
- 125000000466 oxiranyl group Chemical group 0.000 claims description 2
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- 125000003386 piperidinyl group Chemical group 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000003072 pyrazolidinyl group Chemical group 0.000 claims description 2
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 2
- 125000001725 pyrenyl group Chemical group 0.000 claims description 2
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000000719 pyrrolidinyl group Chemical group 0.000 claims description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims description 2
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 30
- 150000002431 hydrogen Chemical group 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 170
- 238000003786 synthesis reaction Methods 0.000 description 170
- 239000007787 solid Substances 0.000 description 64
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 57
- IAFFEFPJCKQBKK-UHFFFAOYSA-N 2,3-dichloro-1-methyl-4-propan-2-ylbenzene;ruthenium Chemical class [Ru].CC(C)C1=CC=C(C)C(Cl)=C1Cl IAFFEFPJCKQBKK-UHFFFAOYSA-N 0.000 description 53
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000010410 layer Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 6
- 230000008033 biological extinction Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- QYTOONVFPBUIJG-UHFFFAOYSA-N azane;cyanic acid Chemical compound [NH4+].[O-]C#N QYTOONVFPBUIJG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 2
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- VFLYBWGSQGMWHP-UHFFFAOYSA-N 3-methyl-1h-imidazol-3-ium;iodide Chemical compound [I-].C[N+]=1C=CNC=1 VFLYBWGSQGMWHP-UHFFFAOYSA-N 0.000 description 2
- KIIHBDSNVJRWFY-UHFFFAOYSA-N 4-bromo-2-(4-bromopyridin-2-yl)pyridine Chemical compound BrC1=CC=NC(C=2N=CC=C(Br)C=2)=C1 KIIHBDSNVJRWFY-UHFFFAOYSA-N 0.000 description 2
- 229920003182 Surlyn® Polymers 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- HMMPCBAWTWYFLR-UHFFFAOYSA-N n-pyridin-2-ylpyridin-2-amine Chemical compound C=1C=CC=NC=1NC1=CC=CC=N1 HMMPCBAWTWYFLR-UHFFFAOYSA-N 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- KKHFRAFPESRGGD-UHFFFAOYSA-N 1,3-dimethyl-7-[3-(n-methylanilino)propyl]purine-2,6-dione Chemical compound C1=NC=2N(C)C(=O)N(C)C(=O)C=2N1CCCN(C)C1=CC=CC=C1 KKHFRAFPESRGGD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GIFWAJGKWIDXMY-UHFFFAOYSA-N 2-octylthiophene Chemical compound CCCCCCCCC1=CC=CS1 GIFWAJGKWIDXMY-UHFFFAOYSA-N 0.000 description 1
- JQUCWIWWWKZNCS-LESHARBVSA-N C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F Chemical compound C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F JQUCWIWWWKZNCS-LESHARBVSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- QOVYHDHLFPKQQG-NDEPHWFRSA-N N[C@@H](CCC(=O)N1CCC(CC1)NC1=C2C=CC=CC2=NC(NCC2=CN(CCCNCCCNC3CCCCC3)N=N2)=N1)C(O)=O Chemical compound N[C@@H](CCC(=O)N1CCC(CC1)NC1=C2C=CC=CC2=NC(NCC2=CN(CCCNCCCNC3CCCCC3)N=N2)=N1)C(O)=O QOVYHDHLFPKQQG-NDEPHWFRSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- WZQSBCHNVPAYOC-UHFFFAOYSA-N chloro(trihexyl)silane Chemical compound CCCCCC[Si](Cl)(CCCCCC)CCCCCC WZQSBCHNVPAYOC-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000002720 diazolyl group Chemical group 0.000 description 1
- BINBUVDYVMWEGQ-UHFFFAOYSA-N dimethoxy(methyl)borane Chemical compound COB(C)OC BINBUVDYVMWEGQ-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- XELZGAJCZANUQH-UHFFFAOYSA-N methyl 1-acetylthieno[3,2-c]pyrazole-5-carboxylate Chemical compound CC(=O)N1N=CC2=C1C=C(C(=O)OC)S2 XELZGAJCZANUQH-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 125000003933 pentacenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C12)* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 230000001443 photoexcitation 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
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical compound CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
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- H—ELECTRICITY
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Abstract
본 발명은 하기 화학식 S로 표시되는 염료 감응 태양 전지용 루테늄계 염료 및 이로부터 제조된 염료 감응 태양 전지에 관한 것이다:
[화학식 S]
본 발명에 따른 루테늄계 염료는 하기 화학식 S의 구조를 갖는 화합물을 포함한다:
[화학식 S]
상기 화학식 S에서 A는
상기 R1은 수소, 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C5~C40의 아릴기, C5~C40의 헤테로아릴기, C5~C40의 아릴옥시기, C1~C40의 알킬옥시기, C5~C40의 아릴아미노기, C5~C40의 디아릴아미노기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기 및 C3~C40의 헤테로시클로알킬기, 실레인기로 이루어진 군에서 선택되거나; 또는 인접하는 기와 축합(fused) 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기이고,
상기 R2는 수소 또는, 상기 R1과 축합(fused) 지방족 고리 또는 축합 헤테로지방족고리를 형성하는 기이다.The present invention relates to a ruthenium-based dye for dye-sensitized solar cells represented by the following formula S and a dye-sensitized solar cell prepared therefrom:
[Formula S]
Ruthenium-based dyes according to the present invention include compounds having the structure of Formula S:
[Formula S]
In Formula S, A is
R1 is hydrogen, deuterium, C1 ~ C40 alkyl group, C2 ~ C40 alkenyl group, C2 ~ C40 alkynyl group, C5 ~ C40 aryl group, C5 ~ C40 heteroaryl group, C5 ~ C40 aryloxy group, C1 ~ C40 alkyloxy group, C5 ~ C40 arylamino group, C5 ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C3 ~ C40 cycloalkyl group, C3 ~ C40 heterocycloalkyl group, silane group Selected from; Or a group which forms a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring with an adjacent group,
R 2 is hydrogen or a group which forms a fused aliphatic ring or a condensed heteroaliphatic ring with R 1.
Description
본 발명은 염료감응태양전지(Dye-Sensitized Solar Cell)에 염료로 사용되는 신규한 루테늄계 염료 및 이로부터 제조되는 염료 감응 태양 전지에 관한 것이다.
The present invention relates to novel ruthenium-based dyes used as dyes in dye-sensitized solar cells and dye-sensitized solar cells prepared therefrom.
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 제조단가가 현저히 낮기 때문에 기존의 비정질 실리콘 태양전지를 대체할 수 있는 가능성을 가지고 있으며, 실리콘태양전지와 달리 염료감응태양전지는 가시광선을 흡수하여 전자-홀쌍을 생성할 수 있는 염료분자와, 생성된 전자를 전달하는 전이금속 산화물을 주 구성 재료로 하는 광전기화학적 태양전지이다.Since the development of the dye-sensitized nanoparticle titanium oxide solar cell 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 their manufacturing costs are significantly lower than conventional silicon-based solar cells. Unlike silicon solar cells, dye-sensitized solar cells absorb visible light It is a photoelectrochemical solar cell whose main constituent material is a dye molecule capable of generating hole pairs and a transition metal oxide that transfers generated electrons.
종래 염료감응태양전지에 사용되는 염료로는 대표적인 것으로는 하기 화합물들을 들 수 있다.Typical dyes used in dye-sensitized solar cells include the following compounds.
*TBA : tetrabutylammonium cation * TBA: tetrabutylammonium cation
그러나 아직도 상기 염료들과 비교하여 산화물 반도체 미립자와의 결합력, 광전기 변환효율, Jsc(shortcircuit photocurrent density) 및 몰 흡광계수를 높여 태양전지의 효율성 및 내구성을 더욱 높일 것이 요청되고 있으며, 새로운 염료에 대한 연구가 필요한 실정이다
However, it is still required to increase the efficiency and durability of solar cells by increasing the bonding force with the oxide semiconductor fine particles, the photoelectric conversion efficiency, the shortcircuit photocurrent density (Jsc) and the molar extinction coefficient compared to the above dyes. Is needed
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 종래의 염료보다 현저히 향상된 광전기변환효율을 나타내며, 산화물 반도체 미립자와의 결합력을 강화시키고, Jsc(short circuit photocurrent density)와 몰 흡광계수가 우수하여 태양전지의 효율을 크게 향상시킬 수 있는 염료 및 이의 제조방법을 제공하는 것을 목적으로 한다.In order to solve the problems of the prior art as described above, the present invention shows a remarkably improved photoelectric conversion efficiency than the conventional dye, enhances the bonding force with the oxide semiconductor fine particles, JSC (short circuit photocurrent density) and the molar extinction coefficient is excellent It is an object of the present invention to provide a dye and a method for producing the same that can greatly improve the efficiency of a solar cell.
또한 본 발명은 상기 염료를 포함하여 현저히 향상된 광전기 변환 효율을 나타내며, 산화물 반도체 미립자와의 결합력이 강화되고, Jsc(short circuit photocurrent density)와 몰 흡광계수가 우수한 염료증감 광전변환소자 및 효율이 현저히 향상된 태양전지를 제공하는 것을 목적으로 한다
In addition, the present invention exhibits a remarkably improved photoelectric conversion efficiency, including the dye, the bonding strength with the oxide semiconductor fine particles, the dye-sensitized photoelectric conversion element and excellent efficiency of the short circuit photocurrent density (Jsc) and the molar extinction coefficient is significantly improved It aims to provide solar cell
본 발명에 따른 루테늄계 염료는 하기 화학식 S의 구조를 갖는 화합물을 포함한다:Ruthenium-based dyes according to the present invention include compounds having the structure of Formula S:
[화학식 S][Chemical Formula S]
상기 화학식 S에서 A는 In Formula S, A is
상기 R1은 R1 is
수소, 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C5~C40의 아릴기, C5~C40의 헤테로아릴기, C5~C40의 아릴옥시기, C1~C40의 알킬옥시기, C5~C40의 아릴아미노기, C5~C40의 디아릴아미노기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기 및 C3~C40의 헤테로시클로알킬기, 실레인기로 이루어진 군에서 선택되거나; 또는 인접하는 기와 축합(fused) 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기이고,
Hydrogen, deuterium, C1-C40 alkyl group, C2-C40 alkenyl group, C2-C40 alkynyl group, C5-C40 aryl group, C5-C40 heteroaryl group, C5-C40 aryloxy group, C1-C40 Alkyloxy group, C5 ~ C40 arylamino group, C5 ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C3 ~ C40 cycloalkyl group and C3 ~ C40 heterocycloalkyl group, silane group or ; Or a group which forms a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring with an adjacent group,
상기 R2는 R2 is
수소 또는, Hydrogen or,
상기 R1과 축합(fused) 지방족 고리 또는 축합 헤테로지방족고리를 형성하는 기이다.
It is a group forming a fused aliphatic ring or a condensed heteroaliphatic ring with R1.
상기 본 발명의 또 다른 과제를 이루기 위하여, 상기 화학식 S로 표시되는 루테늄계 염료로부터 제조되는 염료 감응 태양 전지를 제공한다.In order to achieve another object of the present invention, there is provided a dye-sensitized solar cell prepared from the ruthenium-based dye represented by the formula (S).
본 발명에 따른 신규한 루테늄계 염료 및 이로부터 제조되는 염료 감응 태양 전지는 현저히 향상된 광전기변환효율을 나타내며, 산화물 반도체 미립자와의 결합력을 강화시키고, Jsc(short circuit photocurrent density)와 몰 흡광계수가 우수하여 태양전지의 효율을 크게 향상시킬 수 있다.
The novel ruthenium-based dyes and dye-sensitized solar cells prepared therefrom exhibit significantly improved photovoltaic conversion efficiencies, enhance bonding with oxide semiconductor particles, and have excellent short circuit photocurrent density (Jsc) and molar extinction coefficients. Thus, the efficiency of the solar cell can be greatly improved.
이하 본 발명을 상세히 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 구현예(態樣, aspect)(또는 실시예)들을 본문에 상세하게 설명하고자 한다. 그러나 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. The present invention may be modified in various ways and may have various forms, and thus embodiments (or embodiments) will be described in detail in the text. However, this is not intended to limit the present invention to the specific form disclosed, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.
본 명세서에서 사용한 용어는 단지 특정한 구현예(태양, 態樣, aspect)(또는 실시예)를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, ~포함하다~ 또는 ~이루어진다~ 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, the term " comprising " or " consisting of ", or the like, refers to the presence of a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.
다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.
Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.
본 발명에 따른 염료 감응 태양 전지용 루테늄계 염료는 하기 화학식 S의 구조를 갖는 화합물을 포함한다:Ruthenium-based dyes for dye-sensitized solar cells according to the present invention include a compound having the structure of Formula S:
[화학식 S][Chemical Formula S]
상기 화학식 S에서 A는 In Formula S, A is
상기 R1은 R1 is
수소, 중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C5~C40의 아릴기, C5~C40의 헤테로아릴기, C5~C40의 아릴옥시기, C1~C40의 알킬옥시기, C5~C40의 아릴아미노기, C5~C40의 디아릴아미노기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기 및 C3~C40의 헤테로시클로알킬기, 실레인기로 이루어진 군에서 선택되거나; 또는 인접하는 기와 축합(fused) 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기이고,Hydrogen, deuterium, C1-C40 alkyl group, C2-C40 alkenyl group, C2-C40 alkynyl group, C5-C40 aryl group, C5-C40 heteroaryl group, C5-C40 aryloxy group, C1-C40 Alkyloxy group, C5 ~ C40 arylamino group, C5 ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C3 ~ C40 cycloalkyl group and C3 ~ C40 heterocycloalkyl group, silane group or ; Or a group which forms a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring with an adjacent group,
상기 R2는 R2 is
수소(중수소 포함) 또는, Hydrogen (including deuterium), or
상기 R1과 축합(fused) 지방족 고리 또는 축합 헤테로지방족고리를 형성하는 기이다.
It is a group forming a fused aliphatic ring or a condensed heteroaliphatic ring with R1.
본 발명의 발명자는 상기 화학식 S로 표시되는 화합물에서 R1 및 R2를 특정한, 다양한 유도체를 개발하여 태양 전지에 적용한 결과 현저히 향상된 광전기변환효율을 나타내며, Jsc(short circuit photocurrent density)와 몰 흡광계수가 향상됨을 발견하였다.
The inventors of the present invention show a significantly improved photovoltaic conversion efficiency as a result of applying a variety of derivatives specific to R1 and R2 in the compound represented by Formula S to a solar cell, and improve the short circuit photocurrent density (Jsc) and the molar extinction coefficient. Found.
상기 화학식 S에서 In Formula S
상기 R1의 상기 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C5~C40의 아릴기, C5~C40의 헤테로아릴기, C5~C40의 아릴옥시기, C1~C40의 알킬옥시기, C5~C40의 아릴아미노기, C5~C40의 디아릴아미노기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기 및 C3~C40의 헤테로시클로알킬기, 실레인기는 C1 ~ C40 Alkyl group, C2 ~ C40 Alkenyl group, C2 ~ C40 Alkynyl group, C5 ~ C40 Aryl group, C5 ~ C40 Heteroaryl group, C5 ~ C40 Aryloxy group, C1 ~ C40 Alkyloxy group, C5 ~ C40 arylamino group, C5 ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C3 ~ C40 cycloalkyl group, C3 ~ C40 heterocycloalkyl group, silane group
각각 독립적으로 중수소, 할로겐, 니트릴기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C1~C40의 알콕시기, C1~C40의 아미노기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C40의 아릴기 및 C5~C40의 헤테로아릴기, 실레인기로 이루어진 군에서 선택되는 하나 이상으로 치환되거나 비치환되는 것이 바람직하다.Deuterium, halogen, nitrile group, nitro group, C1-C40 alkyl group, C2-C40 alkenyl group, C1-C40 alkoxy group, C1-C40 amino group, C3-C40 cycloalkyl group, C3-C40 It is preferably substituted or unsubstituted with one or more selected from the group consisting of a heterocycloalkyl group, an aryl group of C6 to C40, a heteroaryl group of C5 to C40, and a silane group.
또 상기 R1은 수소, 페닐기, 톨일기, 비페닐기, 펜타레닐기, 인데닐기, 나프틸기, 비페닐레닐기, 안트라세닐기, 벤조안트라세닐기, 아즈레닐기, 헵타레닐기, 아세나프틸레닐기, 페나레닐기, 메틸안트릴기, 페난트레닐기, 트리페닐레닐기, 피레닐기, 크리세닐기, 피세닐기, 페릴레닐기, 클로로페릴레닐기, 펜타페닐기, 펜타세닐기, 테트라페닐레닐기, 헥사페닐기, 헥사세닐기, 루비세닐기, 코로네닐기, 트리나프틸레닐기, 헵타페닐기, 헵타세닐기, 플루오레닐기, 피란트레닐기, 오바레닐기, 카르바졸릴기, 디벤조퓨라닐기, 디벤조티오페닐기, 티오페닐기, 인돌일기, 푸리닐기, 벤즈이미다졸일기, 퀴놀리닐기, 벤조티오페닐기, 파라티아지닐기, 피롤일기, 피라졸릴기, 이미다졸릴기, 이미다졸리닐기, 옥사졸릴기, 티아졸릴기, 트리아졸릴기, 테트라졸일기, 옥사디아졸릴기, 피리디닐기, 피리다지닐기, 피리미디닐기, 피라지닐기, 티안트레닐기(thianthrenyl), 사이클로펜틸기, 사이클로헥실기, 옥시라닐기, 피롤리디닐기, 피라졸리디닐기, 이미다졸리디닐기, 피페리디닐기, 피페라지닐기, 모르폴리닐기, 디(C6-C50아릴)아미노기, 실레인기 및 이들의 유도체로 이루어진 군으로부터 선택된 것이 바람직하다.
In addition, R1 is hydrogen, phenyl group, tolyl group, biphenyl group, pentarenyl group, indenyl group, naphthyl group, biphenylenyl group, anthracenyl group, benzoanthracenyl group, azurenyl group, heptarenyl group, acenaphthylenyl group , Phenenalenyl group, methyl anthryl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, pisenyl group, perylenyl group, chloroperylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group , Hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptasenyl group, fluorenyl group, pyrantrenyl group, ovarenyl group, carbazolyl group, dibenzofuranyl group, Dibenzothiophenyl group, thiophenyl group, indolyl group, furinyl group, benzimidazolyl group, quinolinyl group, benzothiophenyl group, parathiazinyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, imidazolinyl group, oxa Zolyl group, thiazolyl group, triazolyl group, tetrazolyl group, jade Diazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thianthrenyl, cyclopentyl, cyclohexyl, oxiranyl, pyrrolidinyl, pyrazolidinyl, It is preferably selected from the group consisting of an imidazolidinyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a di (C6-C50 aryl) amino group, a silane group and derivatives thereof.
본 발명은 또한, 전도성 및 투광성을 갖는 기판을 포함하는 제1전극, 상기 제1전극의 어느 한 일면에 형성된 광 흡수층, 상기 광 흡수층이 형성된 제1전극에 대향하여 배치되는 제2전극, 및 상기 제1전극과 제2전극 사이에 위치하는 전해질을 포함하며, 상기 광 흡수층은 반도체 미립자, 및 상기 염료를 포함하는 것인 염료 감응 태양 전지를 제공한다.The present invention also provides a first electrode comprising a substrate having conductivity and light transmittance, a light absorbing layer formed on one surface of the first electrode, a second electrode disposed opposite to the first electrode on which the light absorbing layer is formed, and the It includes an electrolyte located between the first electrode and the second electrode, the light absorbing layer provides a dye-sensitized solar cell comprising a semiconductor fine particle, and the dye.
염료 감응 태양 전지에서 태양 전지가 구동되는 첫 단계는 광에너지로부터 광전하를 생성하는 과정이다. 통상적으로 광전하 생성을 위하여 염료 물질을 사용하는데, 상기 염료 물질은 전도성 투명기판을 투과한 빛을 흡수하여 여기된다.In dye-sensitized solar cells, the first step in driving solar cells is the process of generating photocharges from light energy. Typically, a dye material is used to generate photocharges, and the dye material is excited by absorbing light transmitted through the conductive transparent substrate.
염료 감응 태양 전지 내로 태양광이 입사되면 광양자는 광 흡수층 내 염료 분자에 흡수되고, 이에 따라 염료 분자는 기저상태에서 여기상태로 전자 전이하여 전자-홀쌍을 만든다. 상기 여기상태의 전자는 반도체 미립자 계면의 전도띠(conduction band)로 주입되며, 주입된 전자는 계면을 통해 제1전극으로 전달된다. 이후 외부 회로를 통해 상대 전극인 제2전극으로 이동한다. 한편 전자 전이 결과로 산화된 염료는 전해질층 내 산화-환원 커플의 이온에 의해 환원되고, 산화된 상기 이온은 전하 중성(charge neutrality)을 이루기 위해 제2전극의 계면에 도달한 전자와 환원 반응을 함으로써 상기 염료 감응 태양 전지가 작동하게 된다.When sunlight enters the dye-sensitized solar cell, the photons are absorbed by the dye molecules in the light absorbing layer, whereby the dye molecules electron-transfer from the ground state to the excited state to form electron-hole pairs. Electrons in the excited state are injected into the conduction band of the semiconductor fine particle interface, and the injected electrons are transferred to the first electrode through the interface. After that, it moves to the second electrode which is the counter electrode through the external circuit. On the other hand, the dye oxidized as a result of the electron transfer is reduced by the ions of the redox couple in the electrolyte layer, and the oxidized ions undergo a reduction reaction with the electrons reaching the interface of the second electrode to achieve charge neutrality. The dye-sensitized solar cell is thereby operated.
상기 제1전극으로는 전도성 및 투명성(보다 광범위하게는 투광성)을 갖는 전도성 투명 기판이라면 특별히 한정됨 없이 사용할 수 있다. As the first electrode, any conductive transparent substrate having conductivity and transparency (more broadly transmissive) can be used without particular limitation.
상기 광 흡수층은 반도체 미립자, 및 상기 반도체 미립자에 흡착되며 가시광 흡수로 전자가 여기되는 본 발명의 일 실시형태에 따른 염료를 포함한다.The light absorbing layer includes semiconductor fine particles and a dye according to one embodiment of the present invention in which electrons are excited by absorbing visible light and absorbed by the semiconductor fine particles.
상기 반도체 미립자는 실리콘으로 대표되는 단체 반도체 외에, 금속 산화물, 또는 페로브스카이트 구조를 갖는 복합 금속 산화물 등을 사용할 수 있다. 상기 반도체는 광 여기하에서 전도대 전자가 캐리어로 되어 애노드 전류를 제공하는 n형 반도체인 것이 바람직하다. 구체적으로 예시하면 상기 반도체 미립자로는 Si, TiO2, SnO2,ZnO, WO3, Nb2O5, 또는 TiSrO3 등을 들 수 있으며, 보다 바람직하게는 아나타제형의 TiO2를 사용할 수 있다.
The semiconductor fine particles may be a metal oxide or a composite metal oxide having a perovskite structure, in addition to the single semiconductor represented by silicon. The semiconductor is preferably an n-type semiconductor in which conduction band electrons become carriers under photo excitation to provide an anode current. Specifically, the semiconductor fine particles include Si, TiO 2, SnO 2, ZnO, WO 3, Nb 2 O 5, TiSrO 3, and the like, and more preferably, anatase type TiO 2 may be used.
한편, 본 발명에 따른 염료 감응 태양 전지용 루테늄계 염료는 상기 화학식 S로 표현될 수 있으며, 보다 구체적으로는 화학식 S에서 A는 하기 화학식 1 내지 64로 표현될 수 있다. 상기 화합물들에 대한 구체적인 내용은 상술한 루테늄계 염료에 대하여 설명한 부분과 동일하다.Meanwhile, the ruthenium-based dye for dye-sensitized solar cells according to the present invention may be represented by Chemical Formula S, and more specifically, in Chemical Formula S, A may be represented by Chemical Formulas 1 to 64 below. Details of the compounds are the same as those described for the ruthenium-based dyes described above.
이하에서, 본 발명의 합성예 및 실시예를 구체적으로 예시하지만, 본 발명이 하기의 합성예 및 실시예로 한정되는 것은 아니다. 이하의 합성예에서 중간체 화합물은 최종 생성물의 번호에 일련번호를 추가하는 방식으로 표기한다. 예를 들어, 화합물 1은 화합물 [1] 로 상기 화합물의 중간체 화합물은 [1-1] 등으로 표기한다.Hereinafter, Synthesis Examples and Examples of the present invention will be specifically described, but the present invention is not limited to the following Synthesis Examples and Examples. In the following synthesis examples, the intermediate compounds are indicated by adding the serial number to the final product number. For example, compound 1 is represented by compound [1], and the intermediate compound of the said compound is described by [1-1] etc.
본 명세서에서 화학물의 번호는 화학식의 번호로서 표기한다. 예를 들어, 화학식 1로 표시되는 화합물은 화합물 1로 표기한다.
In the present specification, the chemical number is represented by the chemical number. For example, the compound represented by the formula (1) is represented by compound 1.
[합성 예 1] 화합물 [1]의 합성Synthesis Example 1 Synthesis of Compound [1]
1L플라스크에 1,4-디브로모벤젠 20.0g (84.78mmol)을 무수 테트라히드로퓨란 500mL 로 교반하여 녹이고 -78℃에서 2.5몰-부틸리튬 33.9mL (84.78mmol)을 천천히 적가 시킨다. 동온도에서 15분동안 교반 후 트리부틸 클로로실란 19.9g(84.78mmol)를 천천히 적가시킨다. 반응온도를 상온까지 8시간 동안 서서히 올리고 반응액을 묽은 염산수용액 500mL 에 부어 층 분리시킨다. 유기층을 분리하고 포화 소금물 500mL로 세척한다. 유기층 분리 후 무수황산 마그네슘으로 건조하여 여과한다. 여액을 감압 농축하여 컬럼크로마토그라프로 분리정제하여 중간체 화합물 [1-1] 25.0g (83%)을 수득하였다
To a 1 L flask, 20.0 g (84.78 mmol) of 1,4-dibromobenzene was stirred with 500 mL of anhydrous tetrahydrofuran, and 33.9 mL (84.78 mmol) of 2.5 mol-butyllithium was slowly added dropwise at -78 ° C. After stirring for 15 minutes at the same temperature, 19.9 g (84.78 mmol) of tributyl chlorosilane was slowly added dropwise. The reaction temperature was gradually raised to room temperature for 8 hours, and the reaction solution was poured into 500 mL of diluted aqueous hydrochloric acid solution and the layers were separated. The organic layer is separated and washed with 500 mL of saturated brine. The organic layer was separated and dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 25.0 g (83%) of an intermediate compound [1-1].
둥근바닥플라스크에 디피리딘-2일아민 3.0g(17.52mmol), 중간체 화합물[1-1] 7.47g(21.02mmol), 황산구리(II) 56mg(0.35mmol), 탄산칼륨 3.95g (28.65mmol)을 디페닐에테르 250mL 로 질소 분위기에서 현탁 교반시킨다. 12시간 200℃에서 환류교반한다. 상온으로 냉각시키고 여과한다. 여과액을 감압 농축하고 컬럼크로마토그라프로 분리정제하여 중간체 화합물 [1-2] 3.5g(45%)을 수득하였다.
In a round bottom flask, 3.0 g (17.52 mmol) of dipyridin-2 ylamine, 7.47 g (21.02 mmol) of intermediate compound [1-1] , 56 mg (0.35 mmol) of copper (II) sulfate, and 3.95 g (28.65 mmol) of potassium carbonate were added. It is suspended and stirred in 250 mL of diphenyl ether in nitrogen atmosphere. Stirring reflux at 200 ° C. for 12 hours. Cool to room temperature and filter. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 3.5 g (45%) of the intermediate compound [1-2] .
250mL 2구 반응플라스크에 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) 과 중간체 화합물 [1-2] 1.38g(3.103mmol)을 디메틸포름아미드 100mL 로 현탁 교반시킨다. 약 80℃ 에서 4시간 동안 교반 후 화합물 [1-3] 757mg(3.103mmol) 을 투입시킨다. 4시간 동안 환류 교반 후 냉각하여 티오시안산 암모늄 6.22g (81.65 mmol)을 첨가한다. 반응 온도를 약 130℃에서 4시간 동안 교반 후 상온으로 냉각하여 반응액을 여과한다. 여과액을 감압 농축하여 정제수 100mL, 메탄올 100mL로 세척한다. 고체를 테트라부틸히드록시 암모늄 염 메탄올 용액으로 녹이고 Sephadex LH-20 을 이용하여 컬럼크로마토그라프(전개액 메탄올)로 분리정제한다. 수집된 용액을 묽은 질산 메탄올 용액으로 산성화하여 검은 포도주색 고체의 목적 화합물[1] 1.1g (39%)을 수득하였다.In a 250 mL two-necked reaction flask, 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer and 1.38 g (3.103 mmol) of the intermediate compound [1-2] are suspended and stirred with 100 mL of dimethylformamide. After stirring at about 80 ° C. for 4 hours, 757 mg (3.103 mmol) of Compound [1-3] were added thereto. After stirring for 4 hours at reflux, 6.22 g (81.65 mmol) of ammonium thiocyanate was added. After the reaction temperature was stirred at about 130 ° C. for 4 hours, the reaction solution was filtered by cooling to room temperature. The filtrate was concentrated under reduced pressure and washed with 100 mL of purified water and 100 mL of methanol. The solid is dissolved in tetrabutylhydroxy ammonium salt methanol solution and separated and purified by column chromatography (eluate methanol) using Sephadex LH-20. The collected solution was acidified with dilute methanolic nitrate solution to give 1.1 g (39%) of the desired compound [1] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.05(m, 2H), 8.70(s, 2H), 8.10(m, 2H), 7.50~7.15(m, 12H), 1.30~1.25(m, 18H), 0.87(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.05 (m, 2H), 8.70 (s, 2H), 8.10 (m, 2H), 7.50 ~ 7.15 (m, 12H), 1.30 ~ 1.25 (m, 18H), 0.87 (t, 3H)
MS/FAB : 907(M+)
MS / FAB: 907 (M + )
[합성 예 2] 화합물 [2]의 합성Synthesis Example 2 Synthesis of Compound [2]
합성예 1과 동일한 방법으로 클로로트리헥실실란을 사용하여 수득한 중간체 화합물 [2-1] 1.64g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[2] 1.5g (48%)을 수득하였다.1.64 g (3.103 mmol) of an intermediate compound [2-1] obtained using chlorotrihexylsilane in the same manner as in Synthesis example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and a compound [1- 3] 1.5g (48%) of the desired compound [2] as a dark black solid was obtained using 757 mg (3.103 mmol) and 6.22 g (81.65 mmol) of ammonium thiocyanate.
1H NMR (400 MHz, DMSO-d6) : δ 9.06(m, 2H), 8.65(s, 2H), 8.11(m, 2H), 7.56~7.19(m, 12H), 1.31~1.20(m, 30H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.06 (m, 2H), 8.65 (s, 2H), 8.11 (m, 2H), 7.56 to 7.19 (m, 12H), 1.31 to 1.20 (m, 30H), 0.88 (t, 3H)
MS/FAB : 991(M+)
MS / FAB: 991 (M + )
[합성 예 3] 화합물 [3]의 합성Synthesis Example 3 Synthesis of Compound [3]
둥근바닥플라스크에 디피리딘-2일아민 50.0g(0.292mol), 1,4-디브로모벤젠 138g(0.584mol), 황산구리(II) 932mg(5.84mmol), 탄산칼륨 80.7g (0.584mol)을 디페닐에테르 1L 로 질소 분위기에서 현탁 교반시킨다. 12시간 200℃에서 환류교반한다. 상온으로 냉각시키고 여과한다. 여과액을 감압 농축하고 컬럼크로마토그라프로 분리정제하여 중간체 화합물 [3-1] 75g(78%)을 수득하였다.
In a round bottom flask, 50.0 g (0.292 mol) of dipyridin-2 ylamine, 138 g (0.584 mol) of 1,4-dibromobenzene, 932 mg (5.84 mmol) of copper (II) sulfate, and 80.7 g (0.584 mol) of potassium carbonate were added. It is suspended and stirred in a nitrogen atmosphere with 1 L of diphenyl ether. Stirring reflux at 200 ° C. for 12 hours. Cool to room temperature and filter. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 75 g (78%) of the intermediate compound [3-1] .
500mL 플라스크에 중간체 화합물 [1-1] 5.0g (14.07mmol)을 무수 테트라히드로퓨란 200mL 로 교반하여 녹이고 -78℃에서 2.5몰-부틸리튬 6.7mL (16.88mmol)을 천천히 적가 시킨다. 동온도에서 15분동안 교반 후 트리메틸보론산 1.88mL(16.88mmol)를 천천히 적가시킨다. 반응온도를 상온까지 8시간 동안 서서히 올리고 반응액을 묽은 염산수용액으로 산성화시킨다. 유기층을 분리하고 포화 소금물 300mL로 세척한다. 유기층 분리 후 무수황산 마그네슘으로 건조하여 여과한다. 여액을 감압 농축하여 컬럼크로마토그라프로 분리정제하여 중간체 화합물 [3-2] 3.1g (69%)을 수득하였다
5.0 g (14.07 mmol) of the intermediate compound [1-1] were dissolved in a 500 mL flask by stirring with 200 mL of anhydrous tetrahydrofuran, and 6.7 mL (16.88 mmol) of 2.5 mol-butyllithium was slowly added dropwise at -78 ° C. After stirring for 15 minutes at the same temperature, 1.88 mL (16.88 mmol) of trimethylboronic acid was slowly added dropwise. The reaction temperature is gradually raised to room temperature for 8 hours, and the reaction solution is acidified with diluted aqueous hydrochloric acid solution. The organic layer is separated and washed with 300 mL of saturated brine. The organic layer was separated and dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 3.1 g (69%) of the intermediate compound [3-2].
둥근바닥플라스크에 중간체 화합물[3-1] 2.63g(8.06mmol), 화합물[3-2] 3.1g(9.67mmol), 탄산칼륨 1.67g (12.09mmol)을 1,4-디옥산 200mL 로 현탁 교반시킨다. 테트라키스(트리페닐포스핀)팔라듐 186mg(0.161mmol), 정제수 20mL 가한 후 질소 분위기에서 5시간 동안 환류교반한다. 상온으로 냉각하여 층분리하고 컬럼크로마토그라프로 분리 정제하여 중간체 화합물 [3-3] 2.0g(47%)을 수득하였다.
2.63 g (8.06 mmol) of intermediate compound [3-1] , 3.1 g (9.67 mmol) of compound [3-2] and 1.67 g (12.09 mmol) of potassium carbonate were suspended and stirred in 200 mL of 1,4-dioxane in a round bottom flask. Let's do it. Tetrakis (triphenylphosphine) palladium 186mg (0.161mmol) and 20mL of purified water are added, followed by stirring under reflux for 5 hours in a nitrogen atmosphere. After cooling to room temperature, the layers were separated and purified by column chromatography to obtain 2.0 g (47%) of the intermediate compound [3-3] .
합성예 1과 동일한 방법으로 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 중간체 화합물 [3-3] 1.62g(3.103mmol), 중간체 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은색 고체의 목적 화합물[3] 1.3g (43%)을 수득하였다. In the same manner as in Synthesis Example 1 , ruthenium dichloro (para-cymen) dimer 1.0 g (3.266 mmol), intermediate compound [3-3] 1.62 g (3.103 mmol), intermediate compound [1-3] 757 mg (3.103 mmol), 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 1.3 g (43%) of the desired compound [3] as a black solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.07(m, 2H), 8.71(s, 2H), 8.05(m, 2H), 7.80(m, 2H), 7.55~7.15(m, 14H), 1.31~1.24(m, 18H), 0.89(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.07 (m, 2H), 8.71 (s, 2H), 8.05 (m, 2H), 7.80 (m, 2H), 7.55 ~ 7.15 (m, 14H) , 1.31-1.24 (m, 18H), 0.89 (t, 3H)
MS/FAB : 983(M+)
MS / FAB: 983 (M + )
[합성 예 4] 화합물 [4]의 합성Synthesis Example 4 Synthesis of Compound [4]
합성예 3과 동일한 방법으로 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 중간체 화합물 [4-1] 1.88g(3.103mmol), 중간체 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은색 고체의 목적 화합물[4] 1.0g (30%)을 수득하였다. In the same manner as in Synthesis Example 3 , ruthenium dichloro (para-cymen) dimer 1.0 g (3.266 mmol), intermediate compound [4-1] 1.88 g (3.103 mmol), intermediate compound [1-3] 757 mg (3.103 mmol), 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 1.0 g (30%) of the desired compound [4] as a black solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.05(m, 2H), 8.65(s, 2H), 8.07(m, 2H), 7.81(m, 2H), 7.60~7.15(m, 14H), 1.33~1.20(m, 30H), 0.87(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.05 (m, 2H), 8.65 (s, 2H), 8.07 (m, 2H), 7.81 (m, 2H), 7.60 ~ 7.15 (m, 14H) , 1.33-1.20 (m, 30H), 0.87 (t, 3H)
MS/FAB : 1067(M+)
MS / FAB: 1067 (M + )
[합성 예 5] 화합물 [5]의 합성Synthesis Example 5 Synthesis of Compound [5]
둥근바닥플라스크에 2-옥틸티오펜 10g (50.93mmol)을 무수 테트라히드로 퓨란으로 녹이고 -78℃에서 2.5몰-부틸리튬 24.4mL (61.12mmol)을 천천히 적가 시킨다. 동온도에서 20분동안 교반 후 트리부틸틴클로라이드 16.5mL(61.12mmol)를 천천히 적가시킨다. 반응온도를 상온까지 8시간 동안 서서히 올리고 반응액을 포화 암모늄 수용액에 부어 유기층을 분리다. 유기층 분리 후 무수황산 마그네슘으로 건조하여 여과한다. 여액을 감압 농축하여 중간체 화합물 [5-1] 20.0g (80%)을 수득하였다
In a round bottom flask, 10 g (50.93 mmol) of 2-octylthiophene was dissolved in anhydrous tetrahydrofuran, and 24.4 mL (61.12 mmol) of 2.5 mol-butyllithium was slowly added dropwise at -78 ° C. After stirring for 20 minutes at the same temperature, 16.5 mL (61.12 mmol) of tributyltin chloride was slowly added dropwise. The reaction temperature was gradually raised to room temperature for 8 hours, and the reaction solution was poured into saturated aqueous ammonium solution to separate the organic layer. The organic layer was separated and dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to give 20.0 g (80%) of an intermediate compound [5-1].
둥근바닥플라스크에 중간체 화합물[5-1] 20.0g(41.2mmol), 화합물[3-1] 8.96g(27.46mmol) 을 디메틸포름아미드 300mL 로 녹여 교반시킨다. 테트라키스(트리페닐포스핀)팔라듐 634mg(0.55mmol)을 가한 후 질소 분위기에서 5시간 동안 환류교반한다. 상온으로 냉각하여 층분리하고 컬럼크로마토그라프로 분리 정제하여 중간체 화합물 [5-2] 5.5g(45%)을 수득하였다.
In a round bottom flask, 20.0 g (41.2 mmol) of the intermediate compound [5-1] and 8.96 g (27.46 mmol) of the compound [3-1] are dissolved in 300 mL of dimethylformamide and stirred. Tetrakis (triphenylphosphine) palladium 634 mg (0.55 mmol) was added thereto, followed by stirring under reflux for 5 hours in a nitrogen atmosphere. After cooling to room temperature, the layers were separated and purified by column chromatography to obtain 5.5 g (45%) of the intermediate compound [5-2] .
합성예 1과 동일한 방법으로 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 중간체 화합물 [5-2] 1.37g(3.103mmol), 중간체 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은색 고체의 목적 화합물[5] 0.9g (32%)을 수득하였다.Ruthenium dichloro (para-cymen) dimer 1.0 g (3.266 mmol), intermediate compound [5-2] 1.37 g (3.103 mmol), intermediate compound [1-3] 757 mg (3.103 mmol), in the same manner as in Synthesis example 1 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 0.9 g (32%) of the title compound [5] as a black solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.05(m, 2H), 8.70(s, 2H), 8.10(m, 2H), 7.60~7.10(m, 14H), 2.70(m, 2H), 1.60(m, 2H), 1.29(m, 10H), 0.87(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.05 (m, 2H), 8.70 (s, 2H), 8.10 (m, 2H), 7.60 ~ 7.10 (m, 14H), 2.70 (m, 2H) , 1.60 (m, 2H), 1.29 (m, 10H), 0.87 (t, 3H)
MS/FAB : 903(M+)
MS / FAB: 903 (M + )
[합성 예 6] 화합물 [6]의 합성Synthesis Example 6 Synthesis of Compound [6]
합성예 5와 동일한 방법으로 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 중간체 화합물 [6-1] 1.52g(3.103mmol), 중간체 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은색 고체의 목적 화합물[6] 0.8g (27%)을 수득하였다. In the same manner as in Synthesis Example 5 , ruthenium dichloro (para-cymen) dimer 1.0 g (3.266 mmol), intermediate compound [6-1] 1.52 g (3.103 mmol), intermediate compound [1-3] 757 mg (3.103 mmol), 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 0.8 g (27%) of the desired compound [6] as a black solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.09(m, 2H), 8.69(s, 2H), 8.07(m, 2H), 7.58~7.05(m, 14H), 1.99(m, 2H), 1.30(m, 12H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.09 (m, 2H), 8.69 (s, 2H), 8.07 (m, 2H), 7.58 ~ 7.05 (m, 14H), 1.99 (m, 2H) , 1.30 (m, 12H), 0.88 (t, 3H)
MS/FAB : 949(M+)
MS / FAB: 949 (M + )
[합성 예 7] 화합물 [7]의 합성Synthesis Example 7 Synthesis of Compound [7]
합성예 5와 동일한 방법으로 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 중간체 화합물 [7-1] 1.32g(3.103mmol), 중간체 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은색 고체의 목적 화합물[7] 1.2g (44%)을 수득하였다.Ruthenium dichloro (para-cymen) dimer 1.0 g (3.266 mmol), intermediate compound [7-1] 1.32 g (3.103 mmol), intermediate compound [1-3] 757 mg (3.103 mmol), in the same manner as in Synthesis example 5 . 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 1.2 g (44%) of the desired compound [7] as a black solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.07(m, 2H), 8.70(s, 2H), 8.15(m, 2H), 7.59~7.01(m, 14H), 2.41(m, 2H), 1.55(m, 2H), 1.28(m, 10H), 0.89(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.07 (m, 2H), 8.70 (s, 2H), 8.15 (m, 2H), 7.59-7.01 (m, 14H), 2.41 (m, 2H) , 1.55 (m, 2H), 1.28 (m, 10H), 0.89 (t, 3H)
MS/FAB : 887(M+)
MS / FAB: 887 (M + )
[합성 예 8] 화합물 [8]의 합성Synthesis Example 8 Synthesis of Compound [8]
합성예 5와 동일한 방법으로 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 중간체 화합물 [8-1] 1.52g(3.103mmol), 중간체 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은색 고체의 목적 화합물[8] 1.0g (34%)을 수득하였다. In the same manner as in Synthesis Example 5 , ruthenium dichloro (para-cymen) dimer 1.0 g (3.266 mmol), intermediate compound [8-1] 1.52 g (3.103 mmol), intermediate compound [1-3] 757 mg (3.103 mmol), 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 1.0 g (34%) of the desired compound [8] as a black solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.05(m, 2H), 8.69(s, 2H), 8.15(m, 2H), 7.58~7.11(m, 16H), 2.40(m, 2H), 1.60(m, 2H), 1.28(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.05 (m, 2H), 8.69 (s, 2H), 8.15 (m, 2H), 7.58 ~ 7.11 (m, 16H), 2.40 (m, 2H) , 1.60 (m, 2H), 1.28 (m, 10H), 0.88 (t, 3H)
MS/FAB : 953(M+)
MS / FAB: 953 (M + )
[합성 예 9] 화합물 [9]의 합성Synthesis Example 9 Synthesis of Compound [9]
합성예 5와 동일한 방법으로 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 중간체 화합물 [9-1] 1.62g(3.103mmol), 중간체 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은색 고체의 목적 화합물[9] 1.1g (36%)을 수득하였다.1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, intermediate compound [9-1] 1.62 g (3.103 mmol), intermediate compound [1-3] 757 mg (3.103 mmol), in the same manner as in Synthesis example 5 . 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 1.1 g (36%) of the desired compound [9] as a black solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.07(m, 2H), 8.70(s, 2H), 8.10(m, 2H), 7.80(m, 2H), 7.60~7.20(m, 14H), 2.79(m, 2H), 1.57(m, 2H), 1.30(m, 10H), 0.86(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.07 (m, 2H), 8.70 (s, 2H), 8.10 (m, 2H), 7.80 (m, 2H), 7.60-7.20 (m, 14H) , 2.79 (m, 2H), 1.57 (m, 2H), 1.30 (m, 10H), 0.86 (t, 3H)
MS/FAB : 985(M+)
MS / FAB: 985 (M + )
[합성 예 10] 화합물 [10]의 합성Synthesis Example 10 Synthesis of Compound [10]
합성예 5와 동일한 방법으로 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 중간체 화합물 [10-1] 1.92g(3.103mmol), 중간체 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은색 고체의 목적 화합물[10] 1.3g (39%)을 수득하였다. In the same manner as in Synthesis Example 5 , ruthenium dichloro (para-cymen) dimer 1.0 g (3.266 mmol), intermediate compound [10-1] 1.92 g (3.103 mmol), intermediate compound [1-3] 757 mg (3.103 mmol), 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 1.3 g (39%) of the desired compound [10] as a black solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.05(m, 2H), 8.70(s, 2H), 8.15(m, 2H), 7.59~7.05(m, 16H), 1.20(m, 2H), 1.31(m, 10H), 0.87(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.05 (m, 2H), 8.70 (s, 2H), 8.15 (m, 2H), 7.59 ~ 7.05 (m, 16H), 1.20 (m, 2H) , 1.31 (m, 10H), 0.87 (t, 3H)
MS/FAB : 1078(M+)
MS / FAB: 1078 (M + )
[합성 예 11] 화합물 [11]의 합성Synthesis Example 11 Synthesis of Compound [11]
합성예 5와 동일한 방법으로 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 중간체 화합물 [11-1] 1.54g(3.103mmol), 중간체 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은색 고체의 목적 화합물[11] 1.0g (33%)을 수득하였다. In the same manner as in Synthesis Example 5 , ruthenium dichloro (para-cymen) dimer 1.0 g (3.266 mmol), intermediate compound [11-1] 1.54 g (3.103 mmol), intermediate compound [1-3] 757 mg (3.103 mmol), 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 1.0 g (33%) of the desired compound [11] as a black solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.07(m, 2H), 8.71(s, 2H), 8.13(m, 2H), 7.59~7.11(m, 14H), 2.79(m, 2H), 1.60(m, 2H), 1.28(m, 10H), 0.86(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.07 (m, 2H), 8.71 (s, 2H), 8.13 (m, 2H), 7.59 ~ 7.11 (m, 14H), 2.79 (m, 2H) , 1.60 (m, 2H), 1.28 (m, 10H), 0.86 (t, 3H)
MS/FAB : 959(M+)
MS / FAB: 959 (M + )
[합성 예 12] 화합물 [12]의 합성Synthesis Example 12 Synthesis of Compound [12]
합성예 5와 동일한 방법으로 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 중간체 화합물 [12-1] 1.72g(3.103mmol), 중간체 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은색 고체의 목적 화합물[12] 1.4g (44%)을 수득하였다. In the same manner as in Synthesis Example 5 , ruthenium dichloro (para-cymen) dimer 1.0 g (3.266 mmol), intermediate compound [12-1] 1.72 g (3.103 mmol), intermediate compound [1-3] 757 mg (3.103 mmol), 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 1.4 g (44%) of the desired compound [12] as a black solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.05(m, 2H), 8.70(s, 2H), 8.10(m, 2H), 7.57~7.07(m, 14H), 2.80(m, 2H), 1.59(m, 2H), 1.31(m, 10H), 0.87(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.05 (m, 2H), 8.70 (s, 2H), 8.10 (m, 2H), 7.57 ~ 7.07 (m, 14H), 2.80 (m, 2H) , 1.59 (m, 2H), 1.31 (m, 10H), 0.87 (t, 3H)
MS/FAB : 1015(M+)
MS / FAB: 1015 (M + )
[[
합성예Synthetic example
13] 화합물 [13]의 합성 13] Synthesis of Compound [13]
[ 합성예 5]과 동일한 방법으로 만들어진 중간체화합물 [13-1] 1.55g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-3] 0.75g(3.102mmol), 티오시아네이트 암모늄염 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [13] 0.66g (21%)를 합성하였다.Intermediate produced in the same manner as in Synthesis Example 5] The compound [13-1] 1.55g (3.102mmol), ruthenium dichloro (p-Im men) 1g (3.265mmol), the intermediate compound [1-3] 0.75g (3.102mmol ), 6.6 g (81.648 mmol) of thiocyanate ammonium salt were used to synthesize 0.66 g (21%) of the title compound [13] as a dark red solid.
1H NMR (400 MHz, DMSO-d6) : 9.07(m, 2H), 8.67(s, 2H), 8.12(m, 2H), 7.78(m, 2H), 7.56(m, 2H), 7.38(m, 2H), 6.71~6.63(m, 6H), 2.86(t, 2H), 1.59(t, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.07 (m, 2H), 8.67 (s, 2H), 8.12 (m, 2H), 7.78 (m, 2H), 7.56 (m, 2H), 7.38 ( m, 2H), 6.71-6.63 (m, 6H), 2.86 (t, 2H), 1.59 (t, 2H), 1.31-1.29 (m, 10H), 0.88 (t, 3H)
MS/FAB : 961(M+)
MS / FAB: 961 (M + )
[[
합성예Synthetic example
14] 화합물 [14]의 합성 14] Synthesis of Compound [14]
[ 합성예 5]과 동일한 방법으로 만들어진 중간체화합물 [14-1] 1.69g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-3] 0.75g(3.102mmol), 티오시아네이트 암모늄염 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [14] 0.59g (18%)를 합성하였다.Intermediate produced in the same manner as in Synthesis Example 5] The compound [14-1] 1.69g (3.102mmol), ruthenium dichloro (p-Im men) 1g (3.265mmol), the intermediate compound [1-3] 0.75g (3.102mmol ), 6.21 g (81.648 mmol) of thiocyanate ammonium salt were used to synthesize 0.59 g (18%) of the title compound [14] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06(m, 2H), 8.65(s, 2H), 8.12(m, 2H), 7.92~7.89(m, 2H), 7.55(m, 2H), 7.38~7.33(m, 4H), 6.88(m, 2H), 6.69~6.62(m, 6H), 2.77(t, 2H), 1.59(t, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 (m, 2H), 8.65 (s, 2H), 8.12 (m, 2H), 7.92-7.89 (m, 2H), 7.55 (m, 2H), 7.38-7.33 (m, 4H), 6.88 (m, 2H), 6.69-6.62 (m, 6H), 2.77 (t, 2H), 1.59 (t, 2H), 1.31-1.29 (m, 10H), 0.88 ( t, 3H)
MS/FAB : 1009(M+)
MS / FAB: 1009 (M + )
[[
합성예Synthetic example
15] 화합물 [15]의 합성 15] Synthesis of Compound [15]
[ 합성예 5]과 동일한 방법으로 만들어진 중간체화합물 [15-1] 1.77g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-3] 0.75g(3.102mmol), 티오시아네이트 암모늄염 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [15] 0.87g (26%)를 합성하였다.Intermediate produced in the same manner as in Synthesis Example 5] The compound [15-1] 1.77g (3.102mmol), ruthenium dichloro (p-Im men) 1g (3.265mmol), the intermediate compound [1-3] 0.75g (3.102mmol ), 6.21 g (81.648 mmol) of thiocyanate ammonium salt were used to synthesize 0.87 g (26%) of the title compound [15] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06(m, 2H), 8.66(s, 2H), 8.11(m, 2H), 7.80(d, 2H), 7.55~7.53(m, 4H), 7.38(m, 2H), 6.88(m, 2H), 6.69~6.62(m, 6H), 2.77(t, 2H), 1.59(t, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 (m, 2H), 8.66 (s, 2H), 8.11 (m, 2H), 7.80 (d, 2H), 7.55 ~ 7.53 (m, 4H), 7.38 (m, 2H), 6.88 (m, 2H), 6.69-6.62 (m, 6H), 2.77 (t, 2H), 1.59 (t, 2H), 1.31-1.29 (m, 10H), 0.88 (t, 3H)
MS/FAB : 1033(M+)
MS / FAB: 1033 (M + )
[[
합성예Synthetic example
16] 화합물 [16]의 합성 16] Synthesis of Compound [16]
[ 합성예 1]과 동일한 방법으로 만들어진 중간체화합물 [16-1] 1.71g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-3] 0.75g(3.102mmol), 티오시아네이트 암모늄염 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [16] 0.79g (24%)를 합성하였다. [Synthesis Example 1] The intermediate compound and are made by the same method [16-1] 1.71g (3.102mmol), ruthenium dichloro (p-Im men) 1g (3.265mmol), the intermediate compound [1-3] 0.75g (3.102mmol ), 6.9 g (81.648 mmol) of thiocyanate ammonium salt were used to synthesize 0.79 g (24%) of the title compound [16] .
1H NMR (400 MHz, DMSO-d6) : 9.06(m, 2H), 8.66(s, 2H), 8.11(m, 2H), 7.92~7.87(m, 3H), 7.61~7.55(m, 5H), 7.39~7.35(m, 4H), 6.68~6.62(m, 6H), 2.62(t, 2H), 1.72(s, 6H), 1.59(t, 2H), 1.31~1.28(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 (m, 2H), 8.66 (s, 2H), 8.11 (m, 2H), 7.92 ~ 7.87 (m, 3H), 7.61 ~ 7.55 (m, 5H ), 7.39-7.35 (m, 4H), 6.68-6.62 (m, 6H), 2.62 (t, 2H), 1.72 (s, 6H), 1.59 (t, 2H), 1.31-1.28 (m, 10H), 0.88 (t, 3 H)
MS/FAB : 1013(M+)
MS / FAB: 1013 (M + )
[[
합성예Synthetic example
17] 화합물 [17]의 합성 17] Synthesis of Compound [17]
[ 합성예 1]과 동일한 방법으로 만들어진 중간체화합물 [17-1] 1.97g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-3] 0.75g(3.102mmol), 티오시아네이트 암모늄염 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [17] 1.00g (28%)를 합성하였다. [Synthesis Example 1] The intermediate compound and are made by the same method [17-1] 1.97g (3.102mmol), ruthenium dichloro (p-Im men) 1g (3.265mmol), the intermediate compound [1-3] 0.75g (3.102mmol ), 6.21 g (81.648 mmol) of thiocyanate ammonium salt were used to synthesize 1.00 g (28%) of the title compound [17] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06(m, 2H), 8.66(s, 2H), 8.11(m, 2H), 7.91~7.88(m, 2H), 7.64~7.55(m, 7H), 7.38~7.32(m, 4H), 6.68~6.62(m, 6H), 1.87(t, 4H), 1.31~1.28(m, 24H), 0.88(t, 6H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 (m, 2H), 8.66 (s, 2H), 8.11 (m, 2H), 7.91 ~ 7.88 (m, 2H), 7.64 ~ 7.55 (m, 7H ), 7.38-7.32 (m, 4H), 6.68-6.62 (m, 6H), 1.87 (t, 4H), 1.31-1.28 (m, 24H), 0.88 (t, 6H)
MS/FAB : 1097(M+)
MS / FAB: 1097 (M + )
[[
합성예Synthetic example
18] 화합물 [18]의 합성 18] Synthesis of Compound [18]
[ 합성예 1]과 동일한 방법으로 만들어진 중간체화합물 [18-1] 1.76g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-3] 0.75g(3.102mmol), 티오시아네이트 암모늄염 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [18] 0.84g (25%)를 합성하였다. [Synthesis Example 1] The intermediate compound and are made by the same method [18-1] 1.76g (3.102mmol), ruthenium dichloro (p-Im men) 1g (3.265mmol), the intermediate compound [1-3] 0.75g (3.102mmol ), 6.21 g (81.648 mmol) of thiocyanate ammonium salt were used to synthesize 0.84 g (25%) of the title compound [18] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06(m, 2H), 8.66(s, 2H), 8.11(m, 2H), 7.92~7.88(m, 3H), 7.57~7.37(m, 9H), 6.68~6.63(m, 6H), 2.62(t, 2H), 1.59(t, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H), 0.66(s, 6H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 (m, 2H), 8.66 (s, 2H), 8.11 (m, 2H), 7.92 ~ 7.88 (m, 3H), 7.57 ~ 7.37 (m, 9H ), 6.68-6.63 (m, 6H), 2.62 (t, 2H), 1.59 (t, 2H), 1.31-1.29 (m, 10H), 0.88 (t, 3H), 0.66 (s, 6H)
MS/FAB : 1029(M+)
MS / FAB: 1029 (M + )
[[
합성예Synthetic example
19] 화합물 [19]의 합성 19] Synthesis of Compound [19]
[ 합성예 1]과 동일한 방법으로 만들어진 중간체화합물 [19-1] 2.02g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-3] 0.75g(3.102mmol), 티오시아네이트 암모늄염 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [19] 0.83g (23%)를 합성하였다. [Synthesis Example 1] The intermediate compound and are made by the same method [19-1] 2.02g (3.102mmol), ruthenium dichloro (p-Im men) 1g (3.265mmol), the intermediate compound [1-3] 0.75g (3.102mmol ), 6.21 g (81.648 mmol) of thiocyanate ammonium salt were used to synthesize 0.83 g (23%) of the title compound [19] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06(m, 2H), 8.66(s, 2H), 8.11(m, 2H), 7.87~7.84(m, 3H), 7.60~7.54(m, 6H), 7.37~7.33(m, 4H), 6.70~6.62(m, 6H), 1.45(t, 4H), 1.31~1.29(m, 24H), 0.88(t, 6H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 (m, 2H), 8.66 (s, 2H), 8.11 (m, 2H), 7.87 ~ 7.84 (m, 3H), 7.60 ~ 7.54 (m, 6H ), 7.37-7.33 (m, 4H), 6.70-6.62 (m, 6H), 1.45 (t, 4H), 1.31-1.29 (m, 24H), 0.88 (t, 6H)
MS/FAB : 1113(M+)
MS / FAB: 1113 (M + )
[[
합성예Synthetic example
20] 화합물 [20]의 합성 20] Synthesis of Compound [20]
[ 합성예 1]과 동일한 방법으로 만들어진 중간체화합물 [20-1] 2.07g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-3] 0.75g(3.102mmol), 티오시아네이트 암모늄염 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [20] 0.59g (16%)를 합성하였다. [Synthesis Example 1] The intermediate compound and are made by the same method [20-1] 2.07g (3.102mmol), ruthenium dichloro (p-Im men) 1g (3.265mmol), the intermediate compound [1-3] 0.75g (3.102mmol ), 6.21 g (81.648 mmol) of thiocyanate ammonium salt were used to synthesize 0.59 g (16%) of the title compound [20] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06(m, 2H), 8.66(s, 2H), 8.15~8.12(m, 3H), 7.83~7.79(m, 3H), 7.68~7.65(m, 2H), 7.56~7.54(m, 4H), 7.41~7.38(m, 3H), 7.24(d, 1H), 6.69~6.62(m, 6H), 2.62(t, 2H), 1.72(s, 12H), 1.59(t, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 (m, 2H), 8.66 (s, 2H), 8.15 ~ 8.12 (m, 3H), 7.83 ~ 7.79 (m, 3H), 7.68 ~ 7.65 (m , 2H), 7.56 to 7.54 (m, 4H), 7.41 to 7.38 (m, 3H), 7.24 (d, 1H), 6.69 to 6.62 (m, 6H), 2.62 (t, 2H), 1.72 (s, 12H ), 1.59 (t, 2H), 1.31-1.29 (m, 10H), 0.88 (t, 3H)
MS/FAB : 1129(M+)
MS / FAB: 1129 (M + )
[[
합성예Synthetic example
21] 화합물 [21]의 합성 21] Synthesis of Compound [21]
[ 합성예 1]과 동일한 방법으로 만들어진 중간체화합물 [21-1] 2.17g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-3] 0.75g(3.102mmol), 티오시아네이트 암모늄염 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [21] 0.68g (18%)를 합성하였다. [Synthesis Example 1] The intermediate compound and are made by the same method [21-1] 2.17g (3.102mmol), ruthenium dichloro (p-Im men) 1g (3.265mmol), the intermediate compound [1-3] 0.75g (3.102mmol ), 6.21 g (81.648 mmol) of thiocyanate ammonium salt were used to synthesize 0.68 g (18%) of the title compound [21] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06(m, 2H), 8.66(s, 2H), 8.11(m, 2H), 7.95~7.92(m, 3H), 7.84~7.82(m, 2H), 7.54~7.38(m, 9H), 6.70~6.62(m, 6H), 2.62(t, 2H), 1.59(t, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H), 0.66(s, 12H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 (m, 2H), 8.66 (s, 2H), 8.11 (m, 2H), 7.95 ~ 7.92 (m, 3H), 7.84 ~ 7.82 (m, 2H ), 7.54-7.38 (m, 9H), 6.70-6.62 (m, 6H), 2.62 (t, 2H), 1.59 (t, 2H), 1.31-1.29 (m, 10H), 0.88 (t, 3H), 0.66 (s, 12H)
MS/FAB : 1161(M+)
MS / FAB: 1161 (M + )
[[
합성예Synthetic example
22] 화합물 [22]의 합성 22] Synthesis of Compound [22]
[ 합성예 1]과 동일한 방법으로 만들어진 중간체화합물 [22-1] 1.98g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-3] 0.75g(3.102mmol), 티오시아네이트 암모늄염 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [22] 0.86g (24%)를 합성하였다. [Synthesis Example 1] The intermediate compound and are made by the same method [22-1] 1.98g (3.102mmol), ruthenium dichloro (p-Im men) 1g (3.265mmol), the intermediate compound [1-3] 0.75g (3.102mmol ), 6.21 g (81.648 mmol) of thiocyanate ammonium salt were used to synthesize 0.86 g (24%) of the title compound [22] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06(m, 2H), 8.66(s, 2H), 8.11(m, 2H), 7.53~7.49(m, 4H), 7.06~7.03(m, 4H), 6.69~6.59(m, 8H), 6.39~6.35(m, 4H), 2.62(t, 4H), 1.59(t, 4H), 1.31~1.29(m, 20H), 0.88(t, 6H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 (m, 2H), 8.66 (s, 2H), 8.11 (m, 2H), 7.53 ~ 7.49 (m, 4H), 7.06 ~ 7.03 (m, 4H ), 6.69-6.59 (m, 8H), 6.39-6.35 (m, 4H), 2.62 (t, 4H), 1.59 (t, 4H), 1.31-1.29 (m, 20H), 0.88 (t, 6H)
MS/FAB : 1100(M+)
MS / FAB: 1100 (M + )
[[
합성예Synthetic example
23] 화합물 [23]의 합성 23] Synthesis of Compound [23]
[ 합성예 1]과 동일한 방법으로 만들어진 중간체화합물 [23-1] 1.62g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-3] 0.75g(3.102mmol), 티오시아네이트 암모늄염 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [23] 0.70g (22%)를 합성하였다. [Synthesis Example 1] The intermediate compound and are made by the same method [23-1] 1.62g (3.102mmol), ruthenium dichloro (p-Im men) 1g (3.265mmol), the intermediate compound [1-3] 0.75g (3.102mmol ), 6.21 g (81.648 mmol) of thiocyanate ammonium salt were used to synthesize 0.70 g (22%) of the title compound [23] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06(m, 2H), 8.66(s, 2H), 8.27(d, 1H), 8.13~8.11(m, 3H), 7.77~7.75(m, 2H), 7.55~7.50(m, 5H), 7.36~7.33(m, 4H), 6.68~6.61(m, 6H), 4.16(t, 2H), 1.74(t, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H), 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 (m, 2H), 8.66 (s, 2H), 8.27 (d, 1H), 8.13 ~ 8.11 (m, 3H), 7.77 ~ 7.75 (m, 2H ), 7.55 to 7.50 (m, 5H), 7.36 to 7.33 (m, 4H), 6.68 to 6.61 (m, 6H), 4.16 (t, 2H), 1.74 (t, 2H), 1.31 to 1.29 (m, 10H) ), 0.88 (t, 3H),
MS/FAB : 986(M+)
MS / FAB: 986 (M + )
[합성 예 24] 화합물 [24]의 합성Synthesis Example 24 Synthesis of Compound [24]
합성예 1과 동일한 방법으로 수득한 중간체 화합물 [24-1] 1.86g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[24] 0.97g (28%)을 수득하였다.1.86 g (3.103 mmol) of an intermediate compound [24-1] obtained in the same manner as in Synthesis example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103 mmol) of compound [1-3] 6.22 g (81.65 mmol) of thiocyanate ammonium salt were used to obtain 0.97 g (28%) of the title compound [24] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.16(d, 2H), 8.76(s, 2H), 8.28~8.10(m, 5H), 7.87(s, 1H), 7.68~7.48(m, 13H), 6.80~6.72(m, 6H), 2.72(t, 2H), 1.69(t, 2H), 1.49~1.39(m, 10H), 0.98(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.16 (d, 2H), 8.76 (s, 2H), 8.28-8.10 (m, 5H), 7.87 (s, 1H), 7.68-7.48 (m, 13H ), 6.80-6.72 (m, 6H), 2.72 (t, 2H), 1.69 (t, 2H), 1.49-1.39 (m, 10H), 0.98 (t, 3H)
MS/FAB : 1062(M+)
MS / FAB: 1062 (M + )
[합성 예 25] 화합물 [25]의 합성Synthesis Example 25 Synthesis of Compound [25]
합성예 1과 동일한 방법으로 수득한 중간체 화합물 [25-1] 1.86g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[25] 1.08g (31%)을 수득하였다.1.86 g (3.103 mmol) of an intermediate compound [25-1] obtained in the same manner as in Synthesis example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103 mmol) of compound [1-3] 6.22 g (81.65 mmol) of thiocyanate ammonium salt were used to obtain 1.08 g (31%) of the title compound [25] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.16(d, 2H), 8.76(s, 2H), 8.48~8.42(m, 2H), 8.28~8.21(m, 3H), 7.89(s, 1H), 7.72~7.48(m, 12H), 6.98(d, 1H), 6.80~6.72(m, 6H), 2.72(t, 2H), 1.69(t, 2H), 1.49~1.39(m, 10H), 0.98(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.16 (d, 2H), 8.76 (s, 2H), 8.48-8.42 (m, 2H), 8.28-8.21 (m, 3H), 7.89 (s, 1H ), 7.72-7.48 (m, 12H), 6.98 (d, 1H), 6.80-6.72 (m, 6H), 2.72 (t, 2H), 1.69 (t, 2H), 1.49-1.39 (m, 10H), 0.98 (t, 3 H)
MS/FAB : 1062(M+)
MS / FAB: 1062 (M + )
[합성 예 26] 화합물 [26]의 합성Synthesis Example 26 Synthesis of Compound [26]
합성예 1과 동일한 방법으로 수득한 중간체 화합물 [26-1] 1.63g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[26] 0.97g (30%)을 수득하였다.1.63 g (3.103 mmol) of an intermediate compound [26-1] obtained in the same manner as in Synthesis example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103 mmol) of compound [1-3] , thiocyanate a carbonate salt 6.22g (81.65 mmol) by using the target compound as a dark burgundy solid [26] 0.97g (30%) of the title compound.
1H NMR (400 MHz, DMSO-d6) : 9.16(d, 2H), 8.76(s, 2H), 8.21(d, 2H), 7.91~7.45(m, 11H), 7.15(d, 1H), 6.80~6.72(m, 6H), 2.72(t, 2H), 1.69(t, 2H), 1.49~1.39(m, 10H), 0.98(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.16 (d, 2H), 8.76 (s, 2H), 8.21 (d, 2H), 7.91-7.45 (m, 11H), 7.15 (d, 1H), 6.80-6.72 (m, 6H), 2.72 (t, 2H), 1.69 (t, 2H), 1.49-1.39 (m, 10H), 0.98 (t, 3H)
MS/FAB : 987(M+)
MS / FAB: 987 (M + )
[합성 예 27] 화합물 [27]의 합성Synthesis Example 27 Synthesis of Compound [27]
합성예 1과 동일한 방법으로 수득한 중간체 화합물 [27-1] 1.63g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[27] 0.87g (27%)을 수득하였다.1.63 g (3.103 mmol) of an intermediate compound [27-1] obtained in the same manner as in Synthesis example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103 mmol) of compound [1-3] 6.22 g (81.65 mmol) of thiocyanate ammonium salt were used to obtain 0.87 g (27%) of the title compound [27] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.16(d, 2H), 8.76(s, 2H), 8.21(d, 2H), 7.95~7.37(m, 11H), 7.15(d, 1H), 6.80~6.72(m, 6H), 2.72(t, 2H), 1.69(t, 2H), 1.49~1.39(m, 10H), 0.98(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.16 (d, 2H), 8.76 (s, 2H), 8.21 (d, 2H), 7.95-7.37 (m, 11H), 7.15 (d, 1H), 6.80-6.72 (m, 6H), 2.72 (t, 2H), 1.69 (t, 2H), 1.49-1.39 (m, 10H), 0.98 (t, 3H)
MS/FAB : 987(M+)
MS / FAB: 987 (M + )
[합성 예 28] 화합물 [28]의 합성Synthesis Example 28 Synthesis of Compound [28]
합성예 1과 동일한 방법으로 수득한 중간체 화합물 [28-1] 1.68g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[28] 1.08g (33%)을 수득하였다.1.68 g (3.103 mmol) of an intermediate compound [28-1] obtained in the same manner as in Synthesis example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103 mmol) of compound [1-3] 6.22 g (81.65 mmol) of thiocyanate ammonium salt were used to obtain 1.08 g (33%) of the title compound [28] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.16(d, 2H), 8.76(s, 2H), 8.21(d, 2H), 8.10~7.64(m, 9H), 7.48~7.42(m, 3H), 6.80~6.72(m, 6H), 2.72(t, 2H), 1.69(t, 2H), 1.49~1.39(m, 10H), 0.98(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.16 (d, 2H), 8.76 (s, 2H), 8.21 (d, 2H), 8.10 ~ 7.64 (m, 9H), 7.48 ~ 7.42 (m, 3H ), 6.80-6.72 (m, 6H), 2.72 (t, 2H), 1.69 (t, 2H), 1.49-1.39 (m, 10H), 0.98 (t, 3H)
MS/FAB : 1003(M+)
MS / FAB: 1003 (M + )
[합성 예 29] 화합물 [29]의 합성Synthesis Example 29 Synthesis of Compound [29]
합성예 1과 동일한 방법으로 수득한 중간체 화합물 [29-1] 1.68g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[29] 0.95g (29%)을 수득하였다.1.68 g (3.103 mmol) of an intermediate compound [29-1] obtained in the same manner as in Synthesis example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103 mmol) of compound [1-3] 6.22 g (81.65 mmol) of thiocyanate ammonium salt were used to obtain 0.95 g (29%) of the title compound [29] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.16(d, 2H), 8.76(s, 2H), 8.51(d, 1H), 8.37~8.21(m, 4H), 7.68~7.42(m, 9H), 6.80~6.72(m, 6H), 2.72(t, 2H), 1.69(t, 2H), 1.49~1.39(m, 10H), 0.98(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.16 (d, 2H), 8.76 (s, 2H), 8.51 (d, 1H), 8.37-8.21 (m, 4H), 7.68-7.42 (m, 9H ), 6.80-6.72 (m, 6H), 2.72 (t, 2H), 1.69 (t, 2H), 1.49-1.39 (m, 10H), 0.98 (t, 3H)
MS/FAB : 1003(M+)
MS / FAB: 1003 (M + )
[합성 예 30] 화합물 [30]의 합성Synthesis Example 30 Synthesis of Compound [30]
합성예 1과 동일한 방법으로 수득한 중간체 화합물 [30-1] 1.83g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[30] 0.93g (27%)을 수득하였다.1.83 g (3.103 mmol) of an intermediate compound [30-1] obtained in the same manner as in Synthesis example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103 mmol) of compound [1-3] , 6.22 g (81.65 mmol) of thiocyanate ammonium salt were used to obtain 0.93 g (27%) of the title compound [30] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.16(d, 2H), 8.76(s, 2H), 8.21(d, 2H), 7.95~7.35(m, 12H), 6.80~6.72(m, 6H), 2.72(t, 2H), 1.69(t, 2H), 1.49~1.39(m, 10H), 0.98(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.16 (d, 2H), 8.76 (s, 2H), 8.21 (d, 2H), 7.95 ~ 7.35 (m, 12H), 6.80 ~ 6.72 (m, 6H ), 2.72 (t, 2H), 1.69 (t, 2H), 1.49-1.39 (m, 10H), 0.98 (t, 3H)
MS/FAB : 1050(M+)
MS / FAB: 1050 (M + )
[합성 예 31] 화합물 [31]의 합성Synthesis Example 31 Synthesis of Compound [31]
합성예 1과 동일한 방법으로 수득한 중간체 화합물 [31-1] 1.83g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[31] 1.03g (30%)을 수득하였다.1.83 g (3.103 mmol) of an intermediate compound [31-1] obtained in the same manner as in Synthesis example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymene) dimer, and 758 mg (3.103 mmol) of compound [1-3] , 6.22 g (81.65 mmol) of thiocyanate ammonium salt were used to obtain 1.03 g (30%) of the desired compound [31] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.16(d, 2H), 8.76(s, 2H), 8.21(d, 2H), 7.85~7.48(m, 11H), 7.35(d, 1H), 6.80~6.72(m, 6H), 2.72(t, 2H), 1.69(t, 2H), 1.49~1.39(m, 10H), 0.98(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.16 (d, 2H), 8.76 (s, 2H), 8.21 (d, 2H), 7.85-7.48 (m, 11H), 7.35 (d, 1H), 6.80-6.72 (m, 6H), 2.72 (t, 2H), 1.69 (t, 2H), 1.49-1.39 (m, 10H), 0.98 (t, 3H)
MS/FAB : 1050(M+)
MS / FAB: 1050 (M + )
[합성 예 32] 화합물 [32]의 합성Synthesis Example 32 Synthesis of Compound [32]
합성예 1와 동일한 방법으로 수득한 중간체 화합물 [32-1] 1.48g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[32] 0.86g (28%)을 수득하였다. Synthesis Example 1.48 g (3.103 mmol) of an intermediate compound [32-1] obtained in the same manner as in 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, 758 mg (3.103 mmol) of compound [1-3] , thio 6.22 g (81.65 mmol) of cyanate ammonium salt were used to obtain 0.86 g (28%) of the title compound [32] as a dark red solid.
1H NMR (400 MHz, DMSO-d6) : 9.16(d, 2H), 8.76(s, 2H), 8.21(d, 2H), 7.92(d, 1H), 7.72~7.65(m, 3H), 7.51~7.48(m, 3H), 7.34(d, 1H), 6.80~6.72(m, 6H), 2.72(t, 2H), 1.82(s, 6H), 1.69(t, 2H), 1.49~1.39(m, 10H), 0.98(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.16 (d, 2H), 8.76 (s, 2H), 8.21 (d, 2H), 7.92 (d, 1H), 7.72 ~ 7.65 (m, 3H), 7.51 to 7.48 (m, 3H), 7.34 (d, 1H), 6.80 to 6.72 (m, 6H), 2.72 (t, 2H), 1.82 (s, 6H), 1.69 (t, 2H), 1.49 to 1.39 ( m, 10H), 0.98 (t, 3H)
MS/FAB : 937(M+)
MS / FAB: 937 (M + )
[합성 예 33] 화합물 [33]의 합성Synthesis Example 33 Synthesis of Compound [33]
합성예 1와 동일한 방법으로 수득한 중간체 화합물 [33-1] 1.74g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[33] 1.00g (30%)을 수득하였다. Synthesis Example 1.74 g (3.103 mmol) of an intermediate compound [33-1] obtained in the same manner as in 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, 758 mg (3.103 mmol) of compound [1-3] , thio 6.22 g (81.65 mmol) of cyanate ammonium salt were used to obtain 1.00 g (30%) of the title compound [33] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.16(d, 2H), 8.76(s, 2H), 8.21(d, 2H), 7.97(d, 1H), 7.72~7.65(m, 4H), 7.48~7.38(m, 4H), 6.80~6.72(m, 6H), 1.97(m, 4H), 1.41~1.39(m, 24H), 0.98(m, 6H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.16 (d, 2H), 8.76 (s, 2H), 8.21 (d, 2H), 7.97 (d, 1H), 7.72 ~ 7.65 (m, 4H), 7.48 ~ 7.38 (m, 4H), 6.80 ~ 6.72 (m, 6H), 1.97 (m, 4H), 1.41 ~ 1.39 (m, 24H), 0.98 (m, 6H)
MS/FAB : 1021(M+)
MS / FAB: 1021 (M + )
[합성 예 34] 화합물 [34]의 합성Synthesis Example 34 Synthesis of Compound [34]
합성예 1와 동일한 방법으로 수득한 중간체 화합물 [34-1] 2.71g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[34] 1.18g (27%)을 수득하였다. Synthesis Example 2.71 g (3.103 mmol) of an intermediate compound [34-1] obtained in the same manner as 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, 758 mg (3.103 mmol) of compound [1-3] , thio 6.22 g (81.65 mmol) of cyanate ammonium salt were used to obtain 1.18 g (27%) of the title compound [34] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.16(d, 2H), 8.76(s, 2H), 8.21~8.19(m, 3H), 7.79~7.65(m, 6H), 7.54~7.48(m, 3H), 7.34(d, 1H), 6.80~6.68(m, 6H), 1.97(m, 8H), 1.41~1.39(m, 48H), 0.98(m, 12H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.16 (d, 2H), 8.76 (s, 2H), 8.21-8.19 (m, 3H), 7.79-7.75 (m, 6H), 7.54-7.48 (m , 3H), 7.34 (d, 1H), 6.80-6.68 (m, 6H), 1.97 (m, 8H), 1.41-1.39 (m, 48H), 0.98 (m, 12H)
MS/FAB : 1334(M+)
MS / FAB: 1334 (M + )
[합성 예 35] 화합물 [35]의 합성Synthesis Example 35 Synthesis of Compound [35]
합성예 1와 동일한 방법으로 수득한 중간체 화합물 [35-1] 1.84g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[35] 1.14g (33%)을 수득하였다. Synthesis Example 1.84 g (3.103 mmol) of an intermediate compound [35-1] obtained in the same manner as in 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, 758 mg (3.103 mmol) of compound [1-3] , thio 6.22 g (81.65 mmol) of cyanate ammonium salt were used to obtain 1.14 g (33%) of the title compound [35] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.16(d, 2H), 8.76(s, 2H), 8.21~8.14(m, 3H), 7.87~7.57(m, 6H), 7.48~7.40(m, 3H), 6.80~6.72(m, 6H), 2.72(t, 2H), 1.82(s, 12H), 1.69(t, 2H), 1.41~1.39(m, 10H), 0.98(m, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.16 (d, 2H), 8.76 (s, 2H), 8.21-8.14 (m, 3H), 7.87-7.57 (m, 6H), 7.48-7.40 (m , 3H), 6.80-6.72 (m, 6H), 2.72 (t, 2H), 1.82 (s, 12H), 1.69 (t, 2H), 1.41-1.39 (m, 10H), 0.98 (m, 3H)
MS/FAB : 1053(M+)
MS / FAB: 1053 (M + )
[합성 예 36] 화합물 [36]의 합성Synthesis Example 36 Synthesis of Compound [36]
합성예 1과 동일한 방법을 사용하여 수득한 중간체 화합물 [36-1] 1.53g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[36] 0.9g (29%)을 수득하였다.1.53 g (3.103 mmol) of an intermediate compound [36-1] obtained using the same method as in Synthesis Example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103) of compound [1-3] mmol), ammonium thiocyanate to carbonate 6.22g (81.65 mmol) by using the black burgundy solid of the target compound [36] 0.9g (29%) of the title compound.
1H NMR (400 MHz, DMSO-d6) : δ 9.06~9.05(m, 2H), 8.66(s, 2H), 8.11~8.10(m, 2H), 7.84(d, 1H), 7.64~7.38(m, 7H), 6.80~6.62(m, 6H), 2.62(t, 2H), 1.59~1.58(m, 2H), 1.31~1.29(m, 10H), 0.88(t, 6H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.06-9.05 (m, 2H), 8.66 (s, 2H), 8.11-8.10 (m, 2H), 7.84 (d, 1H), 7.64-7.38 ( m, 7H), 6.80-6.62 (m, 6H), 2.62 (t, 2H), 1.59-1.58 (m, 2H), 1.31-1.29 (m, 10H), 0.88 (t, 6H)
MS/FAB : 953(M+)
MS / FAB: 953 (M + )
[합성 예 37] 화합물 [37]의 합성Synthesis Example 37 Synthesis of Compound [37]
합성예 1과 동일한 방법을 사용하여 수득한 중간체 화합물 [37-1] 1.79g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[37] 0.9g (27%)을 수득하였다.1.79 g (3.103 mmol) of an intermediate compound [37-1] obtained using the same method as in Synthesis Example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103) of compound [1-3] mmol) and 6.22 g (81.65 mmol) of thiocyanate ammonium salt were used to obtain 0.9 g (27%) of the title compound [37] as a dark red solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.06~9.05(m, 2H), 8.66(s, 2H), 8.11~8.10(m, 2H), 7.89(d, 1H), 7.64~7.52(m, 5H), 7.38~7.33(m, 3H), 6.80~6.62(m, 6H), 1.45~1.43(m, 4H), 1.31~1.29(m, 24H), 0.88(t, 6H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.06-9.05 (m, 2H), 8.66 (s, 2H), 8.11-8.10 (m, 2H), 7.89 (d, 1H), 7.64-7.52 ( m, 5H), 7.38-7.33 (m, 3H), 6.80-6.62 (m, 6H), 1.45-1.43 (m, 4H), 1.31-1.29 (m, 24H), 0.88 (t, 6H)
MS/FAB : 1037(M+)
MS / FAB: 1037 (M + )
[합성 예 38] 화합물 [38]의 합성Synthesis Example 38 Synthesis of Compound [38]
합성예 1과 동일한 방법을 사용하여 수득한 중간체 화합물 [38-1] 2.81g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[38] 1.25g (28%)을 수득하였다.2.81 g (3.103 mmol) of an intermediate compound [38-1] obtained using the same method as in Synthesis Example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103) of compound [1-3] mmol), and 6.22 g (81.65 mmol) of thiocyanate ammonium salt were used to obtain 1.25 g (28%) of the title compound [38] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.06~9.05(m, 2H), 8.66(s, 2H), 8.11~8.10(m, 2H), 7.92~7.89(m, 3H), 7.64~7.52(m, 5H), 7.38~7.33(m, 3H), 6.80~6.62(m, 6H), 1.45~1.43(m, 8H), 1.31~1.29(m, 48H), 0.88(t, 12H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.06-9.05 (m, 2H), 8.66 (s, 2H), 8.11-8.10 (m, 2H), 7.92-7.89 (m, 3H), 7.64- 7.52 (m, 5H), 7.38-7.33 (m, 3H), 6.80-6.62 (m, 6H), 1.45-1.43 (m, 8H), 1.31-1.29 (m, 48H), 0.88 (t, 12H)
MS/FAB : 1365(M+)MS / FAB: 1365 (M + )
[합성 예 39] 화합물 [39]의 합성Synthesis Example 39 Synthesis of Compound [39]
합성예 1과 동일한 방법을 사용하여 수득한 중간체 화합물 [39-1] 1.94g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[39] 0.96g (27%)을 수득하였다.1.94 g (3.103 mmol) of an intermediate compound [39-1] obtained using the same method as in Synthesis Example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103) of compound [1-3] mmol), ammonium thiocyanate to carbonate 6.22g (81.65 mmol) by using the black burgundy solid of the target compound [39] 0.96g (27%) of the title compound.
1H NMR (400 MHz, DMSO-d6) : δ 9.06~9.05(m, 2H), 8.66(s, 2H), 8.11~8.10(m, 2H), 7.92(s, 2H), 7.84(d, 1H), 7.64~7.38(m, 7H), 6.80~6.62(m, 6H), 2.62(t, 2H), 1.59~1.58(m, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H), 0.66(s, 12H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.06-9.05 (m, 2H), 8.66 (s, 2H), 8.11-8.10 (m, 2H), 7.92 (s, 2H), 7.84 (d, 1H), 7.64-7.38 (m, 7H), 6.80-6.62 (m, 6H), 2.62 (t, 2H), 1.59-1.58 (m, 2H), 1.31-1.29 (m, 10H), 0.88 (t, 3H), 0.66 (s, 12H)
MS/FAB : 1085(M+)MS / FAB: 1085 (M + )
[합성 예 40] 화합물 [40]의 합성Synthesis Example 40 Synthesis of Compound [40]
합성예 1과 동일한 방법을 사용하여 수득한 중간체 화합물 [40-1] 1.44g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[40] 0.88g (29%)을 수득하였다.1.44 g (3.103 mmol) of an intermediate compound [40-1] obtained using the same method as in Synthesis Example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103) of compound [1-3] mmol), 6.22 g (81.65 mmol) of thiocyanate ammonium salt were used to give 0.88 g (29%) of the desired compound [40] as a dark red solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.06~9.05(m, 2H), 8.66(s, 2H), 8.11~8.04(m, 3H), 7.80(d, 1H), 7.72(d, 1H), 7.55~7.54(m, 2H), 7.38~7.34(m, 3H), 7.06(s, 1H), 6.88(d, 1H), 6.70~6.62(m, 4H), 2.62(t, 2H), 1.59~1.58(m, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.06-9.05 (m, 2H), 8.66 (s, 2H), 8.11-8.04 (m, 3H), 7.80 (d, 1H), 7.72 (d, 1H), 7.55 to 7.54 (m, 2H), 7.38 to 7.74 (m, 3H), 7.06 (s, 1H), 6.88 (d, 1H), 6.70 to 6.62 (m, 4H), 2.62 (t, 2H) , 1.59-1.58 (m, 2H), 1.31-1.29 (m, 10H), 0.88 (t, 3H)
MS/FAB : 927(M+)MS / FAB: 927 (M + )
[합성 예 41] 화합물 [41]의 합성Synthesis Example 41 Synthesis of Compound [41]
합성예 1과 동일한 방법을 사용하여 수득한 중간체 화합물 [41-1] 1.39g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[41] 0.89g (30%)을 수득하였다.1.39 g (3.103 mmol) of an intermediate compound [41-1] obtained using the same method as in Synthesis Example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103) of compound [1-3] mmol), ammonium thiocyanate to carbonate 6.22g (81.65 mmol) by using the target compound as a dark wine-colored solid [41] 0.89g (30%) of the title compound.
1H NMR (400 MHz, DMSO-d6) : δ 9.06~9.05(m, 2H), 8.66(s, 2H), 8.11~8.10(m, 2H), 7.84(d, 1H), 7.64~7.55(m, 3H), 7.43~7.38(m, 3H), 7.23(s, 1H), 6.99(d, 1H), 6.70~6.62(m, 4H), 6.33(d, 1H), 2.62(t, 2H), 1.59~1.58(m, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.06-9.05 (m, 2H), 8.66 (s, 2H), 8.11-8.10 (m, 2H), 7.84 (d, 1H), 7.64-7.55 ( m, 3H), 7.43-7.38 (m, 3H), 7.23 (s, 1H), 6.99 (d, 1H), 6.70-6.62 (m, 4H), 6.33 (d, 1H), 2.62 (t, 2H) , 1.59-1.58 (m, 2H), 1.31-1.29 (m, 10H), 0.88 (t, 3H)
MS/FAB : 911(M+) MS / FAB: 911 (M + )
[합성 예 42] 화합물 [42]의 합성Synthesis Example 42 Synthesis of Compound [42]
합성예 1과 동일한 방법을 사용하여 수득한 중간체 화합물 [42-1] 1.59g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[42] 0.89g (28%)을 수득하였다.1.59 g (3.103 mmol) of an intermediate compound [42-1] obtained using the same method as in Synthesis Example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103) of compound [1-3] mmol), ammonium thiocyanate to carbonate 6.22g (81.65 mmol) by using the target compound as a dark wine-colored solid [42] 0.89g (28%) of the title compound.
1H NMR (400 MHz, DMSO-d6) : δ 9.06~9.05(m, 2H), 8.66(s, 2H), 8.11~8.10(m, 2H), 7.74(d, 1H), 7.55~7.54(m, 3H), 7.38~7.35(m, 3H), 7.2(s, 1H), 6.70~6.5(m, 6H), 2.62(t, 2H), 1.59~1.58(m, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.06-9.05 (m, 2H), 8.66 (s, 2H), 8.11-8.10 (m, 2H), 7.74 (d, 1H), 7.55-7.54 ( m, 3H), 7.38-7.35 (m, 3H), 7.2 (s, 1H), 6.70-6.5 (m, 6H), 2.62 (t, 2H), 1.59-1.58 (m, 2H), 1.31-1.29 ( m, 10H), 0.88 (t, 3H)
MS/FAB : 973(M+)
MS / FAB: 973 (M + )
[합성 예 43] 화합물 [43]의 합성Synthesis Example 43 Synthesis of Compound [43]
합성예 1과 동일한 방법을 사용하여 수득한 중간체 화합물 [43-1] 1.39g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[43] 0.92g (31%)을 수득하였다.1.39 g (3.103 mmol) of an intermediate compound [43-1] obtained using the same method as in Synthesis Example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103) of compound [1-3] mmol) and 6.22 g (81.65 mmol) of thiocyanate ammonium salt were used to obtain 0.92 g (31%) of the title compound [43] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : δ 9.06~9.05(m, 2H), 8.66(s, 2H), 8.12~8.10(m, 3H), 7.77(d, 1H), 7.55~7.50(m, 3H), 7.38~7.23(m, 5H), 6.70~6.62(m, 5H), 4.16(t, 2H), 1.74~1.73(m, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.06-9.05 (m, 2H), 8.66 (s, 2H), 8.12-8.10 (m, 3H), 7.77 (d, 1H), 7.55-7.50 ( m, 3H), 7.38-7.33 (m, 5H), 6.70-6.62 (m, 5H), 4.16 (t, 2H), 1.74-1.73 (m, 2H), 1.31-1.29 (m, 10H), 0.88 ( t, 3H)
MS/FAB : 910(M+)
MS / FAB: 910 (M + )
[합성 예 44] 화합물 [44]의 합성Synthesis Example 44 Synthesis of Compound [44]
합성예 1과 동일한 방법을 사용하여 수득한 중간체 화합물 [44-1] 1.63g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[44] 0.9g (28%)을 수득하였다.1.63 g (3.103 mmol) of an intermediate compound [44-1] obtained using the same method as in Synthesis Example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103) of compound [1-3] mmol), ammonium thiocyanate to carbonate 6.22g (81.65 mmol) by using the target compound as a dark wine-colored solid [44] 0.9g (28%) of the title compound.
1H NMR (400 MHz, DMSO-d6) : δ 9.06~9.05(m, 2H), 8.66(s, 2H), 8.11~8.05(m, 3H), 7.69~7.38(m, 13H), 6.70~6.62(m, 5H), 2.62(t, 2H), 1.59~1.58(m, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.06 ~ 9.05 (m, 2H), 8.66 (s, 2H), 8.11 ~ 8.05 (m, 3H), 7.69 ~ 7.38 (m, 13H), 6.70 ~ 6.62 (m, 5H), 2.62 (t, 2H), 1.59-1.58 (m, 2H), 1.31-1.29 (m, 10H), 0.88 (t, 3H)
MS/FAB : 986(M+) MS / FAB: 986 (M + )
[합성 예 45] 화합물 [45]의 합성Synthesis Example 45 Synthesis of Compound [45]
합성예 1과 동일한 방법을 사용하여 수득한 중간체 화합물 [45-1] 1.63g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[45] 0.93g (29%)을 수득하였다.1.63 g (3.103 mmol) of an intermediate compound [45-1] obtained using the same method as in Synthesis Example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103) of compound [1-3] mmol), ammonium thiocyanate to carbonate 6.22g (81.65 mmol) by using the black burgundy solid of the target compound [45] 0.93g (29%) of the title compound.
1H NMR (400 MHz, DMSO-d6) : δ 9.06~9.05(m, 2H), 8.66(s, 2H), 8.38~8.32(m, 2H), 8.11~8.03(m, 3H), 7.58~7.38(m, 9H), 6.86(d, 1H), 6.70~6.62(m, 6H), 2.62(t, 2H), 1.59~1.58(m, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.06-9.05 (m, 2H), 8.66 (s, 2H), 8.38-8.32 (m, 2H), 8.11-8.03 (m, 3H), 7.58- 7.38 (m, 9H), 6.86 (d, 1H), 6.70-6.62 (m, 6H), 2.62 (t, 2H), 1.59-1.58 (m, 2H), 1.31-1.29 (m, 10H), 0.88 ( t, 3H)
MS/FAB : 986(M+) MS / FAB: 986 (M + )
[[
합성예Synthetic example
46] 화합물 [46]의 합성 46] Synthesis of Compound [46]
합성예 1과 동일한 방법을 사용하여 수득한 중간체 화합물 [46-1] 1.39g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol), 화합물 [1-3] 758mg(3.103mmol), 티오시아네이트 암모늄염 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[46] 0.89g (30%)을 수득하였다.1.39 g (3.103 mmol) of an intermediate compound [46-1] obtained using the same method as in Synthesis Example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 758 mg (3.103) of compound [1-3] mmol), ammonium thiocyanate to carbonate 6.22g (81.65 mmol) by using the target compound as a dark wine-colored solid [46] 0.89g (30%) of the title compound.
1H NMR (400 MHz, DMSO-d6) : δ 9.06~9.05(m, 2H), 8.66(s, 2H), 8.17~8.03(m, 4H), 7.59~7.55(m, 3H), 7.42~7.38(m, 4H), 6.70~6.62(m, 6H), 4.16(t, 2H), 1.74~1.73(m, 2H), 1.31~1.29(m, 10H), 0.88(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): δ 9.06-9.05 (m, 2H), 8.66 (s, 2H), 8.17-8.03 (m, 4H), 7.59-7.55 (m, 3H), 7.42- 7.38 (m, 4H), 6.70-6.62 (m, 6H), 4.16 (t, 2H), 1.74-1.73 (m, 2H), 1.31-1.29 (m, 10H), 0.88 (t, 3H)
MS/FAB : 910(M+)
MS / FAB: 910 (M + )
[합성 예 47] 화합물 [47]의 합성Synthesis Example 47 Synthesis of Compound [47]
합성예 1과 동일한 방법으로 2-디피리디닐아민을 사용하여 수득한 중간체 화합물 [47-1] 2.15g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-5] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[47] 0.98g (27%)을 수득하였다.2.15 g (3.103 mmol) of an intermediate compound [47-1] obtained by using 2-dipyridinylamine in the same manner as in Synthesis example 1 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and a compound [ 1-5] 0.98 g (27%) of the desired compound [47] as a dark brown solid was obtained using 757 mg (3.103 mmol) and 6.22 g (81.65 mmol) of ammonium thiocyanate.
1H NMR (400 MHz, DMSO-d6) : 9.06~9.08(m, 4H), 8.11(d, 2H), 7.70(d, 2H), 7.44(t, 2H), 7.23(d, 2H), 7.00(s, 4H), 6.70(d, 2H), 6.52(d, 2H), 6.60(t, 2H), 1.29~1.33(m, 30H), 0.96 1 H NMR (400 MHz, DMSO-d 6 ): 9.06-9.08 (m, 4H), 8.11 (d, 2H), 7.70 (d, 2H), 7.44 (t, 2H), 7.23 (d, 2H), 7.00 (s, 4H), 6.70 (d, 2H), 6.52 (d, 2H), 6.60 (t, 2H), 1.29 ~ 1.33 (m, 30H), 0.96
(m, 9H) (m, 9H)
MS/FAB : 1156(M+)
MS / FAB: 1156 (M + )
[합성 예 48] 화합물 [48]의 합성Synthesis Example 48 Synthesis of Compound [48]
500ml 플라스크에 N-(4'-톨릴)-N,N-디(2-피리딜)아민 10g (38.3mmol), 7-트리헥실실릴비티오페닐-2-알데히드 11.7g (42.13mmol), 디메틸포름아미드 100ml를 넣어 교반한다. 무수 칼륨 t-부톡사이드 15.6g (45.96mmol)를 10분동안 투입한다. 상온에서 2시간 교반시킨다. 반응 완료 후 반응기에 물150ml와 에틸아세테이트 150ml를 투입하여 추출한다. 유기층 무수 황산 마그네슘으로 건조하여 여과한다. 감압농축하여 용매제거한 다음, 디클로로메탄과 노르말헥산을 이용하여 재결정하여 중간체 화합물 [48-1] 11.2g(21.47mmol)을 수득하였다. In a 500ml flask 10 g (38.3 mmol) N- (4'-tolyl) -N, N-di (2-pyridyl) amine, 11.7 g (42.13 mmol) of 7-trihexylsilylbithiophenyl-2-aldehyde, 100 ml of dimethylformamide Put and stir. 15.6 g (45.96 mmol) of anhydrous potassium t-butoxide is added for 10 minutes. Stir at room temperature for 2 hours. After completion of the reaction, 150ml of water and 150ml of ethyl acetate were added to the reactor and extracted. The organic layer was dried over anhydrous magnesium sulfate and filtered. After concentration under reduced pressure, the solvent was removed, and then recrystallized with dichloromethane and normal hexane to obtain 11.2 g (21.47 mmol) of an intermediate compound [48-1] .
..
2-디피리디닐아민을 사용하여 수득한 중간체 화합물 [48-1] 2.23g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-5] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[48] 1.05g (29%)을 수득하였다.2.23 g (3.103 mmol) of an intermediate compound [48-1] obtained using 2-dipyridinylamine, 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 757 mg (3.103) of compound [1-5] mmol) and 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 1.05 g (29%) of the title compound [48] as a dark red solid.
1H NMR (400 MHz, DMSO-d6) : 9.06~9.08(m, 4H), 8.11(d, 2H), 7.70(d, 2H), 7.44(t, 2H), 7.05(d, 2H), 7.00(m, 4H), 6.99(s, 2H), 6.70(d, 2H), 6.60(t, 2H), 6.41(d, 2H), 1.29~1.33(m, 30H), 0.96(m, 9H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06-9.08 (m, 4H), 8.11 (d, 2H), 7.70 (d, 2H), 7.44 (t, 2H), 7.05 (d, 2H), 7.00 (m, 4H), 6.99 (s, 2H), 6.70 (d, 2H), 6.60 (t, 2H), 6.41 (d, 2H), 1.29-1.33 (m, 30H), 0.96 (m, 9H)
MS/FAB : 1182(M+)
MS / FAB: 1182 (M + )
[합성 예 49] 화합물 [49]의 합성Synthesis Example 49 Synthesis of Compound [49]
합성예 48과 동일한 방법으로 2-디피리디닐아민을 사용하여 수득한 중간체 화합물 [49-1] 1.96g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-5] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[49] 1.0g (30%)을 수득하였다.1.96 g (3.103 mmol) of an intermediate compound [49-1] obtained using 2-dipyridinylamine in the same manner as in Synthesis example 48 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and a compound [ 1-5] 1.0 g (30%) of the desired compound [49] as a dark brown solid was obtained using 757 mg (3.103 mmol) and 6.22 g (81.65 mmol) of ammonium thiocyanate.
1H NMR (400 MHz, DMSO-d6) : 9.06~9.08(m, 4H), 8.11(d, 2H), 7.70(d, 2H), 7.40~7.48 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 ~ 9.08 (m, 4H), 8.11 (d, 2H), 7.70 (d, 2H), 7.40 ~ 7.48
(m, 6H), 7.17(d, 2H), 6.99(s, 2H), 6.70(d, 2H), 6.60(t, 2H), 6.46(d, 2H), 1.29~1.33(m, 30H), 0.96(m, 9H), (m, 6H), 7.17 (d, 2H), 6.99 (s, 2H), 6.70 (d, 2H), 6.60 (t, 2H), 6.46 (d, 2H), 1.29-1.33 (m, 30H), 0.96 (m, 9 H),
MS/FAB : 1093(M+)
MS / FAB: 1093 (M + )
[합성 예 50] 화합물 [50]의 합성Synthesis Example 50 Synthesis of Compound [50]
합성예 48과 동일한 방법으로 2-디피리디닐아민을 사용하여 수득한 중간체 화합물 [50-1] 1.45g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-5] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[50] 0.77g (27%)을 수득하였다.1.45 g (3.103 mmol) of an intermediate compound [50-1] obtained using 2-dipyridinylamine in the same manner as in Synthesis example 48 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and a compound [ 1-5] 0.77 g (27%) of the title compound [50] as a dark brown solid was obtained using 757 mg (3.103 mmol) and 6.22 g (81.65 mmol) of ammonium thiocyanate.
1H NMR (400 MHz, DMSO-d6) : 9.06~9.08(m, 4H), 8.11(d, 2H), 7.70(d, 2H), 7.44(t, 2H), 7.05(d, 2H), 6.99(s, 2H), 6.70(m, 3H), 6.60(m, 3H), 6.41(d, 2H), 2.55(t, 2H), 1.62(m, 2H), 1.29~1.33(m, 10H), 0.96(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06-9.08 (m, 4H), 8.11 (d, 2H), 7.70 (d, 2H), 7.44 (t, 2H), 7.05 (d, 2H), 6.99 (s, 2H), 6.70 (m, 3H), 6.60 (m, 3H), 6.41 (d, 2H), 2.55 (t, 2H), 1.62 (m, 2H), 1.29-1.33 (m, 10H) , 0.96 (t, 3H)
MS/FAB : 929(M+)
MS / FAB: 929 (M + )
[합성 예 51] 화합물 [51]의 합성Synthesis Example 51 Synthesis of Compound [51]
합성예 48과 동일한 방법으로 2-디피리디닐아민을 사용하여 수득한 중간체 화합물 [51-1] 1.71g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-5] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[51] 1.21g (39%)을 수득하였다.1.71 g (3.103 mmol) of an intermediate compound [51-1] obtained using 2-dipyridinylamine in the same manner as in Synthesis example 48 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and a compound [ 1-5] 1.21 g (39%) of the target compound [51] as a dark red solid was obtained using 757 mg (3.103 mmol) and 6.22 g (81.65 mmol) of ammonium thiocyanate.
1H NMR (400 MHz, DMSO-d6) : 9.06~9.08(m, 4H), 8.11(d, 2H), 7.70(d, 2H), 7.44(t, 2H), 7.05(d, 2H), 7.00(d, 2H), 6.99(s, 2H), 6.70(m, 3H), 6.60(m, 3H), 6.41(d, 2H), 2.55(t, 2H), 1.62(m, 2H), 1.29~1.33(m, 10H), 0.96(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06-9.08 (m, 4H), 8.11 (d, 2H), 7.70 (d, 2H), 7.44 (t, 2H), 7.05 (d, 2H), 7.00 (d, 2H), 6.99 (s, 2H), 6.70 (m, 3H), 6.60 (m, 3H), 6.41 (d, 2H), 2.55 (t, 2H), 1.62 (m, 2H), 1.29 ~ 1.33 (m, 10H), 0.96 (t, 3H)
MS/FAB : 1011(M+)
MS / FAB: 1011 (M + )
[합성 예 52] 화합물 [52]의 합성Synthesis Example 52 Synthesis of Compound [52]
합성예 48과 동일한 방법으로 2-디피리디닐아민을 사용하여 수득한 중간체 화합물 [52-1] 1.63g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-5] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[52] 0.88g (29%)을 수득하였다.1.63 g (3.103 mmol) of an intermediate compound [52-1] obtained using 2-dipyridinylamine in the same manner as in Synthesis example 48 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and a compound [ 1-5] 0.88 g (29%) of the title compound [52] was obtained as a black wine solid using 757 mg (3.103 mmol) and 6.22 g (81.65 mmol) of ammonium thiocyanate.
1H NMR (400 MHz, DMSO-d6) : 9.06~9.08(m, 4H), 8.11(d, 2H), 7.70(d, 2H), 7.44(t, 2H), 6.99~7.05(m, 5H), 6.70(d, 2H), 6.60(m, 3H), 6.41(d, 2H), 2.55(t, 2H), 1.62(m, 2H), 1.29~1.33(m, 10H), 0.96(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 ~ 9.08 (m, 4H), 8.11 (d, 2H), 7.70 (d, 2H), 7.44 (t, 2H), 6.99 ~ 7.05 (m, 5H ), 6.70 (d, 2H), 6.60 (m, 3H), 6.41 (d, 2H), 2.55 (t, 2H), 1.62 (m, 2H), 1.29-1.33 (m, 10H), 0.96 (t, 3H)
MS/FAB : 985(M+)
MS / FAB: 985 (M + )
[합성 예 53] 화합물 [53]의 합성Synthesis Example 53 Synthesis of Compound [53]
합성예 48과 동일한 방법으로 2-디피리디닐아민을 사용하여 수득한 중간체 화합물 [53-1] 1.80g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-5] 757mg(3.103mmol), 티오시안산 암모늄 6.22g (81.65 mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[53] 0.75g (23%)을 수득하였다.1.80 g (3.103 mmol) of an intermediate compound [53-1] obtained using 2-dipyridinylamine in the same manner as in Synthesis example 48 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and a compound [ 1-5] 0.75 g (23%) of the title compound (53 ) was obtained as a black wine solid using 757 mg (3.103 mmol) and 6.22 g (81.65 mmol) of ammonium thiocyanate.
1H NMR (400 MHz, DMSO-d6) : 9.06~9.08(m, 4H), 8.11(d, 2H), 7.70(d, 2H), 7.44(t, 2H), 6.99~7.05(m, 5H), 6.70(d, 2H), 6.60(m, 3H), 6.41(d, 2H), 2.55(t, 2H), 1.62(m, 2H), 1.29~1.33(m, 10H), 0.96(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 ~ 9.08 (m, 4H), 8.11 (d, 2H), 7.70 (d, 2H), 7.44 (t, 2H), 6.99 ~ 7.05 (m, 5H ), 6.70 (d, 2H), 6.60 (m, 3H), 6.41 (d, 2H), 2.55 (t, 2H), 1.62 (m, 2H), 1.29-1.33 (m, 10H), 0.96 (t, 3H)
MS/FAB : 1041(M+)
MS / FAB: 1041 (M + )
[[ 합성예Synthetic example 54] 화합물 [54]의 합성 54] Synthesis of Compound [54]
합성예 48과 동일한 방법으로 2-디피리디닐아민을 사용하여 수득한 중간체 화합물 [54-1] 1.78g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-5] 0.75g(3.102mmol), 티오시안산 암모늄 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [54] 1.11g (35%)를 합성하였다.1.78 g (3.102 mmol) of an intermediate compound [54-1] obtained by using 2-dipyridinylamine in the same manner as in Synthesis example 48 , 1 g (3.265 mmol) of ruthenium dichloro (para-cymen), an intermediate compound [1 -5] 0.75 g (3.102 mmol), 6.11 g (81.648 mmol) of ammonium thiocyanate were used to synthesize 1.11 g (35%) of the title compound [54] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06~9.08(m, 4H), 8.11(d, 2H), 7.90 (s, 1H), 7.80(s, 1H), 7.70(d, 2H), 7.44(t, 2H), 7.3(s, 1H), 6.93~7.05(m, 5H), 6.70(d, 2H), 6.60(t, 2H), 6.41(d, 2H), 2.55(t, 2H), 1.62(m, 2H), 1.29~1.33(m, 10H), 0.96(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06-9.08 (m, 4H), 8.11 (d, 2H), 7.90 (s, 1H), 7.80 (s, 1H), 7.70 (d, 2H), 7.44 (t, 2H), 7.3 (s, 1H), 6.93 ~ 7.05 (m, 5H), 6.70 (d, 2H), 6.60 (t, 2H), 6.41 (d, 2H), 2.55 (t, 2H) , 1.62 (m, 2H), 1.29-1.33 (m, 10H), 0.96 (t, 3H)
MS/FAB : 1035(M+)
MS / FAB: 1035 (M + )
[[
합성예Synthetic example
55] 화합물 [55]의 합성 55] Synthesis of Compound [55]
합성예 48과 동일한 방법으로 2-디피리디닐아민을 사용하여 수득한 중간체 화합물 [55-1] 1.79g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-5] 0.75g(3.102mmol), 티오시안산 암모늄 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [55] 1.1g (34%)를 합성하였다.1.79 g (3.102 mmol) of an intermediate compound [55-1] obtained using 2-dipyridinylamine in the same manner as in Synthesis example 48 , 1 g (3.265 mmol) of ruthenium dichloro (para-cymen), an intermediate compound [1 -5] 0.75 g (3.102 mmol), 6.21 g (81.648 mmol) of ammonium thiocyanate were used to synthesize 1.1 g (34%) of the title compound [55] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06~9.08(m, 4H), 8.11(d, 2H), 7.79~7.84(m, 2H), 7.70~7.71(m, 3H), 7.54(d, 1H), 7.41~7.44(m, 3H), 7.17~7.24(m, 3H), 6.99(s, 2H), 6.70(d, 2H), 6.60(t, 2H), 6.46(d, 2H), 2.55(t, 2H), 1.67 (s, 6H), 1.62(m, 2H), 1.29~1.33(m, 10H), 0.96(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 ~ 9.08 (m, 4H), 8.11 (d, 2H), 7.79 ~ 7.84 (m, 2H), 7.70 ~ 7.71 (m, 3H), 7.54 (d , 1H), 7.41-7.44 (m, 3H), 7.17-7.44 (m, 3H), 6.99 (s, 2H), 6.70 (d, 2H), 6.60 (t, 2H), 6.46 (d, 2H), 2.55 (t, 2H), 1.67 (s, 6H), 1.62 (m, 2H), 1.29-1.33 (m, 10H), 0.96 (t, 3H)
MS/FAB : 1039(M+)
MS / FAB: 1039 (M + )
[[
합성예Synthetic example
56] 화합물 [56]의 합성 56] Synthesis of Compound [56]
합성예 48과 동일한 방법으로 2-디피리디닐아민을 사용하여 수득한 중간체 화합물 [56-1] 2.05g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-5] 0.75g(3.102mmol), 티오시안산 암모늄 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [56] 1.0g (29%)를 합성하였다.2.05 g (3.102 mmol) of an intermediate compound [56-1] obtained using 2-dipyridinylamine in the same manner as in Synthesis example 48 , 1 g (3.265 mmol) of ruthenium dichloro (para-cymen), an intermediate compound [1 -5] 0.75 g (3.102 mmol), 6.21 g (81.648 mmol) of ammonium thiocyanate were used to synthesize 1.0 g (29%) of the title compound [56] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06~9.08(m, 4H), 8.11(d, 2H), 7.84(s, 2H), 7.70~7.71(m, 3H), 7.55(d, 1H), 7.54(d, 1H), 7.38~7.44(m, 3H), 7.28(t, 1H), 7.17(d, 2H), 6.99(s, 2H), 6.70(d, 2H), 6.60(t, 2H), 6.46(d, 2H), 1.87(t, 4H), 1.29~1.33(m, 24H), 0.96(t, 6H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 ~ 9.08 (m, 4H), 8.11 (d, 2H), 7.84 (s, 2H), 7.70 ~ 7.71 (m, 3H), 7.55 (d, 1H ), 7.54 (d, 1H), 7.38-7.44 (m, 3H), 7.28 (t, 1H), 7.17 (d, 2H), 6.99 (s, 2H), 6.70 (d, 2H), 6.60 (t, 2H), 6.46 (d, 2H), 1.87 (t, 4H), 1.29-1.33 (m, 24H), 0.96 (t, 6H)
MS/FAB : 1123(M+)
MS / FAB: 1123 (M + )
[[
합성예Synthetic example
57] 화합물 [57]의 합성 57] Synthesis of Compound [57]
합성예 48과 동일한 방법으로 4-(트리프로필살릴)페닐보론산, 4,4'-다이브로모-2,2'-바이피리딘을 사용하여 만들어진 중간체 화합물 [57-1] 2.10g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-5] 0.75g(3.102mmol), 티오시안산 암모늄 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [57] 0.7g (20%)를 합성하였다.2.10 g (3.102 mmol) of an intermediate compound [57-1] prepared using 4- (tripropylsalyl) phenylboronic acid and 4,4'-dibromo-2,2'-bipyridine in the same manner as in Synthesis example 48 , Ruthenium dichloro (para-cymen) 1 g (3.265 mmol), intermediate compound [1-5] 0.75 g (3.102 mmol), By using ammonium thiocyanate, 6.21g (81.648mmol) was synthesized target compound as a dark burgundy solid [57] 0.7g (20%) .
1H NMR (400 MHz, DMSO-d6) : 9.06~9.08(m, 4H), 8.11(d, 2H), 7.76(s, 1H), 7.70(d, 2H), 7.58~7.60(m, 4H), 7.42~7.44(m, 3H), 7.32(m, 1H), 7.17(m, 2H), 6.99(s, 2H), 6.70(d, 2H), 6.60(t, 2H), 6.46(d, 2H), 1.29~1.45(m, 28H), 0.96(t, 6H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06 ~ 9.08 (m, 4H), 8.11 (d, 2H), 7.76 (s, 1H), 7.70 (d, 2H), 7.58 ~ 7.60 (m, 4H ), 7.42-7.44 (m, 3H), 7.32 (m, 1H), 7.17 (m, 2H), 6.99 (s, 2H), 6.70 (d, 2H), 6.60 (t, 2H), 6.46 (d, 2H), 1.29-1.45 (m, 28H), 0.96 (t, 6H)
MS/FAB : 1139(M+)
MS / FAB: 1139 (M + )
[[
합성예Synthetic example
58] 화합물 [58]의 합성 58] Synthesis of Compound [58]
합성예 48과 동일한 방법으로 4-(트리메틸살릴)페닐보론산, 4,4'-다이브로모-2,2'-바이피리딘을 사용하여 만들어진 중간체 화합물 [58-1] 2.15g(3.102mmol), 루테늄디클로로(파라-싸이멘) 1g(3.265mmol), 중간체화합물 [1-5] 0.75g(3.102mmol), 티오시안산 암모늄 6.21g(81.648mmol)을 사용하여 검은 포도주색고체의 목적화합물 [58] 0.9g (25%)를 합성하였다.2.15 g (3.102 mmol) of an intermediate compound [58-1], prepared by using 4- (trimethylsalyl) phenylboronic acid, 4,4'-dibromo-2,2'-bipyridine in the same manner as in Synthesis example 48 , Ruthenium dichloro (para-cymen) 1 g (3.265 mmol), intermediate compound [1-5] 0.75 g (3.102 mmol), 6.21 g (81.648 mmol) of ammonium thiocyanate were used to synthesize 0.9 g (25%) of the title compound (58 ) as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.06~9.08(m, 4H), 8.11(d, 2H), 8.01(d, 1H), 7.84(d, 1H), 7.77(s, 1H), 7.71(s, 1H), 7.70(d, 2H), 7.69(s, 1H), 7.54(d, 1H), 7.44~7.47(m, 3H), 7.30(d, 1H), 7.17(d, 2H), 6.99(s, 2H), 6.70(d, 2H), 6.60(t, 2H), 6.46(d, 2H), 2.55(t, 2H), 1.67(s, 12H), 1.62(t, 2H), 1.29~1.33(m, 10H), 0.96(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.06-9.08 (m, 4H), 8.11 (d, 2H), 8.01 (d, 1H), 7.84 (d, 1H), 7.77 (s, 1H), 7.71 (s, 1H), 7.70 (d, 2H), 7.69 (s, 1H), 7.54 (d, 1H), 7.44-7.47 (m, 3H), 7.30 (d, 1H), 7.17 (d, 2H) , 6.99 (s, 2H), 6.70 (d, 2H), 6.60 (t, 2H), 6.46 (d, 2H), 2.55 (t, 2H), 1.67 (s, 12H), 1.62 (t, 2H), 1.29-1.33 (m, 10H), 0.96 (t, 3H)
MS/FAB : 1155(M+)
MS / FAB: 1155 (M + )
[[ 합성예Synthetic example 59] 화합물 [59]의 합성 59] Synthesis of Compound [59]
합성예 48와 동일한 방법을 사용하여 수득한 중간체 화합물 [59-1] 1.71g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g(81.65mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[59] 1.06g (32%)을 수득하였다. Synthesis Example 1.71 g (3.103 mmol) of an intermediate compound [59-1] obtained using the same method as 48 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 757 mg (3.103 mmol) of compound [1-3] , to give the thio when Ansan ammonium 6.22g (81.65mmol) 1.06g black wine target compound [59] in the color solid using (32%).
1H NMR (400 MHz, DMSO-d6) : 9.04(d, 2H), 8.64(s, 2H), 8.19(s, 2H), 8.09~8.10(m, 3H), 7.75(d, 3H), 7.48~7.53(m, 4H), 7.36(d, 2H), 7.27(t, 1H), 7.15(d, 1H), 6.93(s, 2H), 6.68(d, 2H), 6.60~6.61(m, 4H), 4.14(t, 2H), 1.72(m, 2H), 1.27~1.29(m, 10H), 0.86(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.04 (d, 2H), 8.64 (s, 2H), 8.19 (s, 2H), 8.09-8.10 (m, 3H), 7.75 (d, 3H), 7.48 ~ 7.53 (m, 4H), 7.36 (d, 2H), 7.27 (t, 1H), 7.15 (d, 1H), 6.93 (s, 2H), 6.68 (d, 2H), 6.60 ~ 6.61 (m, 4H), 4.14 (t, 2H), 1.72 (m, 2H), 1.27-1.29 (m, 10H), 0.86 (t, 3H)
MS/FAB : 1012(M+)
MS / FAB: 1012 (M + )
[[ 합성예Synthetic example 60] 화합물 [60]의 합성 60] Synthesis of Compound [60]
합성예 48와 동일한 방법을 사용하여 수득한 중간체 화합물 [60-1] 1.94g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g(81.65mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[60] 1.00g (28%)을 수득하였다. Synthesis Example 1.94 g (3.103 mmol) of an intermediate compound [60-1] obtained using the same method as 48 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 757 mg (3.103 mmol) of compound [1-3] 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 1.00 g (28%) of the title compound [60] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.04(d, 2H), 8.64(s, 2H), 8.93(s, 1H), 8.09(d, 2H), 8.03(s,1H), 7.92(d, 1H), 7.75(d, 2H), 7.43~7.56(m, 9H), 7.36(d, 2H), 7.06(d, 1H), 6.93(s, 2H), 6.68(d, 2H), 6.60~6.61(m, 4H), 2.60(t, 2H), 1.57(m, 4H), 1.27~1.29(m, 10H), 0.86(t, 3H), 1 H NMR (400 MHz, DMSO-d 6 ): 9.04 (d, 2H), 8.64 (s, 2H), 8.93 (s, 1H), 8.09 (d, 2H), 8.03 (s, 1H), 7.92 ( d, 1H), 7.75 (d, 2H), 7.43 ~ 7.56 (m, 9H), 7.36 (d, 2H), 7.06 (d, 1H), 6.93 (s, 2H), 6.68 (d, 2H), 6.60 ~ 6.61 (m, 4H), 2.60 (t, 2H), 1.57 (m, 4H), 1.27-1.29 (m, 10H), 0.86 (t, 3H),
MS/FAB : 1088(M+)
MS / FAB: 1088 (M + )
[ [ 합성예Synthetic example ] 화합물 [61]의 합성Synthesis of Compound [61]
합성예 48와 동일한 방법을 사용하여 수득한 중간체 화합물 [61-1] 2.06g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g(81.65mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[61] 1.06g (29%)을 수득하였다. Synthesis Example 2.06 g (3.103 mmol) of an intermediate compound [61-1] obtained using the same method as 48 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 757 mg (3.103 mmol) of compound [1-3] 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 1.06 g (29%) of the title compound [61] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.04(d, 2H), 8.64(s, 2H), 8.19(s, 1H), 8.09(d, 2H), 8.03(s, 1H), 7.75(d, 2H), 7.53~7.56(m, 4H), 7.43(d, 1H), 7.36(d, 2H), 7.15(d, 1H), 6.93(s, 2H), 6.68(d, 2H), 6.60~6.61(m, 4H), 4.14(t, 2H), 2.60(t, 2H), 1.72(m, 2H), 1.57(m, 2H), 1.27~1.29(m, 20H), 0.86(t, 6H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.04 (d, 2H), 8.64 (s, 2H), 8.19 (s, 1H), 8.09 (d, 2H), 8.03 (s, 1H), 7.75 ( d, 2H), 7.53 to 7.56 (m, 4H), 7.43 (d, 1H), 7.36 (d, 2H), 7.15 (d, 1H), 6.93 (s, 2H), 6.68 (d, 2H), 6.60 ~ 6.61 (m, 4H), 4.14 (t, 2H), 2.60 (t, 2H), 1.72 (m, 2H), 1.57 (m, 2H), 1.27-1.29 (m, 20H), 0.86 (t, 6H )
MS/FAB : 1124(M+)
MS / FAB: 1124 (M + )
[[ 합성예Synthetic example 62] 화합물 62의 합성 62] Synthesis of Compound 62
합성예 48와 동일한 방법을 사용하여 수득한 중간체 화합물 [62-1] 1.39g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g(81.65mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[62] 1.01g (34%)을 수득하였다. Synthesis Example 1.39 g (3.103 mmol) of an intermediate compound [62-1] obtained using the same method as 48 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and 757 mg (3.103 mmol) of compound [1-3] , to give the thio when Ansan ammonium 6.22g (81.65mmol) 1.01g black wine target compound [62] in the color solid using (34%).
1H NMR (400 MHz, DMSO-d6) : 9.04(d, 2H), 8.64(s, 2H), 8.09(d, 2H), 7.42~7.75(m, 4H), 7.53(t, 2H), 7.36(d, 2H), 6.97(d, 2H), 6.93(s, 2H), 6.68(d, 2H), 6.60~6.61(m, 4H), 4.04(t, 2H), 1.74(m, 2H), 1.41(m, 2H), 1.27~1.29(m, 4H), 0.86(t, 3H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.04 (d, 2H), 8.64 (s, 2H), 8.09 (d, 2H), 7.42 ~ 7.75 (m, 4H), 7.53 (t, 2H), 7.36 (d, 2H), 6.97 (d, 2H), 6.93 (s, 2H), 6.68 (d, 2H), 6.60-6.61 (m, 4H), 4.04 (t, 2H), 1.74 (m, 2H) , 1.41 (m, 2H), 1.27-1.29 (m, 4H), 0.86 (t, 3H)
MS/FAB : 911(M+)
MS / FAB: 911 (M + )
[[ 합성예Synthetic example 63] 화합물 63의 합성 63] Synthesis of Compound 63
합성예 48와 동일한 방법을 사용하여 수득한 중간체 화합물 [63-1] 2.30g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g(81.65mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[63] 1.02g (26%)을 수득하였다. Synthesis Example 2.30 g (3.103 mmol) of an intermediate compound [63-1] obtained using the same method as 48 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and [ 757 ] 757 mg (3.103 mmol) of dimer ( 1-3 ) 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 1.02 g (26%) of the title compound [63] as a dark brown solid.
1H NMR (400 MHz, DMSO-d6) : 9.04(d, 2H), 8.64(s, 2H), 8.09(d, 2H), 7.75(d, 4H), 7.53(t, 2H), 7.36(d, 2H), 7.02(d, 4H), 6.93(s, 2H), 6.68(d, 2H), 6.56~6.61(m, 8H), 6.60(t, 4H), 1.57(m, 4H), 1.27~1.29(m, 20H), 0.86(t, 6H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.04 (d, 2H), 8.64 (s, 2H), 8.09 (d, 2H), 7.75 (d, 4H), 7.53 (t, 2H), 7.36 ( d, 2H), 7.02 (d, 4H), 6.93 (s, 2H), 6.68 (d, 2H), 6.56 ~ 6.61 (m, 8H), 6.60 (t, 4H), 1.57 (m, 4H), 1.27 ~ 1.29 (m, 20H), 0.86 (t, 6H)
MS/FAB : 1202(M+)
MS / FAB: 1202 (M + )
[[ 합성예Synthetic example 64] 화합물 64의 합성 64] Synthesis of Compound 64
합성예 48와 동일한 방법을 사용하여 수득한 중간체 화합물 [64-1] 1.52g(3.103mmol), 루테늄디클로로(파라-싸이멘) 다이머 1.0g(3.266mmol) , 화합물 [1-3] 757mg(3.103mmol), 티오시안산 암모늄 6.22g(81.65mmol)을 사용하여 검은 포도주색 고체의 목적 화합물[64] 0.99g (32%)을 수득하였다. Synthesis Example 1.52 g (3.103 mmol) of an intermediate compound [64-1] obtained using the same method as 48 , 1.0 g (3.266 mmol) of ruthenium dichloro (para-cymen) dimer, and [ 757 ] 757 mg (3.103 mmol) of dimer ( 1-3 ) 6.22 g (81.65 mmol) of ammonium thiocyanate were used to obtain 0.99 g (32%) of the title compound [64] as a dark red solid.
1H NMR (400 MHz, DMSO-d6) : 9.04(d, 2H), 8.64(s, 2H), 8.09(d, 2H), 7.75~7.77(m, 4H), 7.53~7.54(m, 4H), 7.36(d, 2H), 6.93(s, 2H), 6.68(d, 2H), 6.60~6.61(m, 4H), 5.7(s, 1H), 4.26(s, 4H) 1 H NMR (400 MHz, DMSO-d 6 ): 9.04 (d, 2H), 8.64 (s, 2H), 8.09 (d, 2H), 7.75 ~ 7.77 (m, 4H), 7.53 ~ 7.54 (m, 4H ), 7.36 (d, 2H), 6.93 (s, 2H), 6.68 (d, 2H), 6.60-6.61 (m, 4H), 5.7 (s, 1H), 4.26 (s, 4H)
MS/FAB : 951(M+)
MS / FAB: 951 (M + )
비교예Comparative example
1 : 염료 감응 태양 전지의 제조 1: Manufacture of Dye-Sensitized Solar Cells
Fluorine-doped tin oxide (FTO) 위에 입경 5 내지 15nm 정도 크기의 산화 티타늄 분산액을 닥터블레이드법으로 2cm2 면적에 도포하고, 450℃에서 30분간 열처리 소성공을 통해 20㎛ 두께의 다공성 산화 티타늄 후막을 제작하였다. 그 후 상온에서 시편을 하기 비교샘플 1을 에탄올에 0.3mM 농도로 용해시킨 염료분산액에 침지하여 염료 흡착 처리를 24시간 이상 실시하였다.
A titanium oxide dispersion having a particle size of 5 to 15 nm on a fluorine-doped tin oxide (FTO) was applied to a 2 cm 2 area by a doctor blade method, and a porous titanium oxide thick film having a thickness of 20 μm was formed through a heat-treatment calciner at 450 ° C. for 30 minutes. Produced. Thereafter, the specimen was immersed in a dye dispersion solution of Comparative Sample 1 dissolved in ethanol at a concentration of 0.3 mM at room temperature, and then the dye adsorption treatment was performed for 24 hours or more.
이후 염료가 흡착된 다공성 산화 티타늄 후막을 에탄올을 이용하여 세척하고 상온건조하여 광흡수층이 형성된 제 1전극을 제조하였다.
Thereafter, the porous titanium oxide thick film to which the dye was adsorbed was washed with ethanol and dried at room temperature to prepare a first electrode having a light absorption layer.
Fluorine-doped tin oxide (FTO) 위에 스핀 코팅법을 이용하여 약 200nm 두께로 백금층을 형성하였고, 전해액 주입을 위해 0.75mm 직경의 드릴을 이용하여 두 개의 미세 구멍을 만들어 제 2전극을 제조하였다.
A platinum layer was formed to a thickness of about 200 nm on the fluorine-doped tin oxide (FTO) by spin coating, and a second electrode was prepared by making two micropores using a 0.75 mm diameter drill for electrolyte injection.
그 다음으로 제 1 전극과 제 2 전극을 SURLYN(열가소성 고분자 필름)으로 이루어지는 약 40~60㎛ 두께의 고분자 격벽을 사이에 두고 배치한 후 약 150℃의 가열판 상에서 약 1~2기압으로 압착시켜 제 1전극과 제 2 전극 사이에 밀폐된 공간을 형성한다.
Next, the first electrode and the second electrode were disposed with a polymer partition wall having a thickness of about 40 to 60 μm made of SURLYN (thermoplastic polymer film), and then pressed at about 1 to 2 atm on a heating plate of about 150 ° C. A sealed space is formed between the first electrode and the second electrode.
제 2전극의 미세구멍에 0.6M의 1-헥실-2,3-메틸-이미다졸리움 아이오다이드, 0.1M LiI, 0.05M I2 및 0.5M 4-tert-부틸-피리딘(TBP)을 아세토나이트릴에 용해시킨 I3/I 의 전해질 용액을 주입하여태양전지를 제조하였다.
0.6M 1-hexyl-2,3-methyl-imidazolium iodide, 0.1M LiI, 0.05MI 2 and 0.5M 4-tert-butyl-pyridine (TBP) were injected into the micropores of the second electrode. A solar cell was prepared by injecting an electrolyte solution of I 3 / I dissolved in a reel.
평가예Evaluation example : 비교샘플 1 Comparative Sample 1
비교예 1 에서 제조된 염료 감응 태양전지에 대하여 광전류 전압을 측정하고, 측정된 광전류 곡선으로부터 개방전압 (open-circuit voltage: Voc), 전류 밀도(short-circuit current: Jsc) 및 충진계수(fill factor:FF)를 계산하였다, 또한 광전환효율을 위의 값을 이용하여 산출하였다.
The photocurrent voltage of the dye-sensitized solar cell manufactured in Comparative Example 1 was measured, and an open-circuit voltage (Voc), a short-circuit current (Jsc), and a fill factor were measured from the measured photocurrent curve. : FF) was calculated and the light conversion efficiency was calculated using the above values.
이때 광원으로는 제논 램프(xenon lamp, Newport, 66142 500W)을 사용하였으며, 상기 제논 램프의 태양 조건(AM 1.5)은 표준 태양 전지(National Renewable Energy ㅊLaboratory, A2LA accreditation certificate # 2236.01, Type of material: Mono-Si + BK7 필터)를 사용하여 보정하였다.
The xenon lamp (Newen, Newport, 66142 500W) was used as the light source, and the solar condition (AM 1.5) of the xenon lamp was a standard solar cell (National Renewable Energy Laboratory, A2LA accreditation certificate # 2236.01, Type of material: Mono-Si + BK7 filter).
이로부터 계산된 전류밀도(Isc), 전압(Voc) 및 충진계수(fill factor, FF), 광전변환효율(ηe)을 하기 표 1에 나타내었다.The calculated current density (Isc), voltage (Voc) and fill factor (FF), the photoelectric conversion efficiency (ηe) calculated from this are shown in Table 1 below.
표 1Table 1
실시예Example
1 : 염료 감응 태양 전지의 제조 1: Manufacture of Dye-Sensitized Solar Cells
Fluorine-doped tin oxide (FTO) 위에 입경 5 내지 15nm 정도 크기의 산화 티타늄 분산액을 닥터블레이드법으로 2cm2 면적에 도포하고, 450℃에서 30분간 열처리 소성공을 통해 20㎛ 두께의 다공성 산화 티타늄 후막을 제작하였다. 그 후 상온에서 시편을 하기 화학식1~62을 에탄올에 0.3mM 농도로 용해시킨 염료분산액에 침지하여 염료 흡착 처리를 24시간 이상 실시하였다.
A titanium oxide dispersion having a particle size of 5 to 15 nm on a fluorine-doped tin oxide (FTO) was applied to a 2 cm 2 area by a doctor blade method, and a porous titanium oxide thick film having a thickness of 20 μm was formed through a heat-treatment calciner at 450 ° C. for 30 minutes. Produced. Thereafter, the specimens were immersed in a dye dispersion in which the following Chemical Formulas 1 to 62 were dissolved in ethanol at a concentration of 0.3 mM, and then the dye adsorption treatment was performed for 24 hours or more.
이후 염료가 흡착된 다공성 산화 티타늄 후막을 에탄올을 이용하여 세척하고 상온건조하여 광흡수층이 형성된 제 1전극을 제조하였다.
Thereafter, the porous titanium oxide thick film to which the dye was adsorbed was washed with ethanol and dried at room temperature to prepare a first electrode having a light absorption layer.
Fluorine-doped tin oxide (FTO) 위에 스핀 코팅법을 이용하여 약 200nm 두께로 백금층을 형성하였고, 전해액 주입을 위해 0.75mm 직경의 드릴을 이용하여 두 개의 미세 구멍을 만들어 제 2전극을 제조하였다.
A platinum layer was formed to a thickness of about 200 nm on the fluorine-doped tin oxide (FTO) by spin coating, and a second electrode was prepared by making two micropores using a 0.75 mm diameter drill for electrolyte injection.
그 다음으로 제 1 전극과 제 2 전극을 SURLYN(열가소성 고분자 필름)으로 이루어지는 약 40~60㎛ 두께의 고분자 격벽을 사이에 두고 배치한 후 약 150℃의 가열판 상에서 약 1~2기압으로 압착시켜 제 1전극과 제 2 전극 사이에 밀폐된 공간을 형성한다.
Next, the first electrode and the second electrode were disposed with a polymer partition wall having a thickness of about 40 to 60 μm made of SURLYN (thermoplastic polymer film), and then pressed at about 1 to 2 atm on a heating plate of about 150 ° C. A sealed space is formed between the first electrode and the second electrode.
제 2전극의 미세구멍에 0.6M의 1-헥실-2,3-메틸-이미다졸리움 아이오다이드, 0.1M LiI, 0.05M I2 및 0.5M 4-tert-부틸-피리딘(TBP)을 아세토나이트릴에 용해시킨 I3/I 의 전해질 용액을 주입하여태양전지를 제조하였다.
0.6M 1-hexyl-2,3-methyl-imidazolium iodide, 0.1M LiI, 0.05MI 2 and 0.5M 4-tert-butyl-pyridine (TBP) were injected into the micropores of the second electrode. A solar cell was prepared by injecting an electrolyte solution of I 3 / I dissolved in a reel.
평가예Evaluation example : 화학식 1~62의 특성 평가 : Characterization of Chemical Formulas 1-62
실시예 1 내지 62에서 제조된 염료 감응 태양전지에 대하여 광전류 전압을 측정하고, 측정된 광전류 곡선으로부터 개방전압 (open-circuit voltage: Voc), 전류 밀도(short-circuit current: Jsc) 및 충진계수(fill factor:FF)를 계산하였다, 또한 광전환효율을 위의 값을 이용하여 산출하였다.
The photocurrent voltages of the dye-sensitized solar cells prepared in Examples 1 to 62 were measured, and the open-circuit voltage (Voc), the short-circuit current (Jsc) and the filling factor (from the measured photocurrent curve) were measured. fill factor (FF) was calculated, and the light conversion efficiency was calculated using the above values.
이때 광원으로는 제논 램프(xenon lamp, Newport, 66142 500W)을 사용하였으며, 상기 제논 램프의 태양 조건(AM 1.5)은 표준 태양 전지(National Renewable Energy Laboratory, A2LA accreditation certificate # 2236.01, Type of material: Mono-Si + BK7 필터)를 사용하여 보정하였다.In this case, a xenon lamp (xenon lamp, Newport, 66142 500W) was used as the light source, and the solar condition (AM 1.5) of the xenon lamp was a standard solar cell (National Renewable Energy Laboratory, A2LA accreditation certificate # 2236.01, Type of material: Mono -Si + BK7 filter).
이로부터 계산된 전류밀도(Isc), 전압(Voc) 및 충진계수(fill factor, FF), 광전변환효율(ηe)을 하기 표 2에 나타내었다.The calculated current density (Isc), voltage (Voc) and fill factor (FF), the photoelectric conversion efficiency (ηe) calculated from this are shown in Table 2 below.
표 2Table 2
이상의 설명에서 태양전지, 염료감응성 특징, 염료 등과 관련된 통상의 공지된 기술을 생략되어 있으나, 당업자라면 용이하게 이를 추측 및 추론하고 재현할 수 있다.In the above description, although the conventionally known techniques related to solar cells, dye-sensitized features, dyes, and the like are omitted, those skilled in the art can easily infer, infer, and reproduce them.
또 이상에서 본 발명을 설명함에 있어 첨부된 실시예들을 참조하여 특정 구조를 갖는 화합물을 위주로 설명하였으나 본 발명은 당업자에 의하여 다양한 수정, 변경 및 치환이 가능하고, 이러한 수정, 변경 및 치환은 본 발명의 보호범위에 속하는 것으로 해석되어야 한다.
In addition, in the above description of the present invention, the compounds having a specific structure have been described with reference to the accompanying examples, but the present invention can be variously modified, changed, and replaced by those skilled in the art, and such modifications, changes, and substitutions may be made by the present invention. It should be interpreted as falling within the protection scope of.
Claims (5)
[화학식 S]
(상기 화학식 S에서 A는
상기 R1은
중수소, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C5~C40의 아릴기, C5~C40의 헤테로아릴기, C5~C40의 아릴옥시기, C1~C40의 알킬옥시기, C5~C40의 아릴아미노기, C5~C40의 디아릴아미노기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기 및 C3~C40의 헤테로시클로알킬기, 실레인기로 이루어진 군에서 선택되거나; 또는 인접하는 기와 축합(fused) 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기이고,
상기 R2는
수소 또는,
상기 R1과 축합(fused) 지방족 고리 또는 축합 헤테로지방족고리를 형성하는 기이다)Ruthenium-based dye for dye-sensitized solar cells comprising a compound having the structure of Formula S.
[Formula S]
(A in Formula S is
R1 is
Deuterium, C1-C40 alkyl group, C2-C40 alkenyl group, C2-C40 alkynyl group, C5-C40 aryl group, C5-C40 heteroaryl group, C5-C40 aryloxy group, C1-C40 alkyl Oxy group, C5 ~ C40 arylamino group, C5 ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C3 ~ C40 cycloalkyl group, C3 ~ C40 heterocycloalkyl group, silane group; Or a group which forms a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring with an adjacent group,
R2 is
Hydrogen or,
Is a group forming a fused aliphatic ring or a condensed heteroaliphatic ring with R1)
상기 R1의 상기 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C5~C40의 아릴기, C5~C40의 헤테로아릴기, C5~C40의 아릴옥시기, C1~C40의 알킬옥시기, C5~C40의 아릴아미노기, C5~C40의 디아릴아미노기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기 및 C3~C40의 헤테로시클로알킬기, 실레인기는
각각 독립적으로 중수소, 할로겐, 니트릴기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C1~C40의 알콕시기, C1~C40의 아미노기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C40의 아릴기 및 C5~C40의 헤테로아릴기, 실레인기로 이루어진 군에서 선택되는 하나 이상으로 치환되거나 비치환되는 것을 특징으로 하는 염료 감응 태양 전지용 루테늄계 염료.The method of claim 1,
C1 ~ C40 Alkyl group, C2 ~ C40 Alkenyl group, C2 ~ C40 Alkynyl group, C5 ~ C40 Aryl group, C5 ~ C40 Heteroaryl group, C5 ~ C40 Aryloxy group, C1 ~ C40 Alkyloxy group, C5 ~ C40 arylamino group, C5 ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C3 ~ C40 cycloalkyl group, C3 ~ C40 heterocycloalkyl group, silane group
Deuterium, halogen, nitrile group, nitro group, C1-C40 alkyl group, C2-C40 alkenyl group, C1-C40 alkoxy group, C1-C40 amino group, C3-C40 cycloalkyl group, C3-C40 A ruthenium-based dye for dye-sensitized solar cells, which is unsubstituted or substituted with one or more selected from the group consisting of a heterocycloalkyl group, an aryl group of C6 to C40, a heteroaryl group of C5 to C40, and a silane group.
상기 R1은 페닐기, 톨일기, 비페닐기, 펜타레닐기, 인데닐기, 나프틸기, 비페닐레닐기, 안트라세닐기, 벤조안트라세닐기, 아즈레닐기, 헵타레닐기, 아세나프틸레닐기, 페나레닐기, 메틸안트릴기, 페난트레닐기, 트리페닐레닐기, 피레닐기, 크리세닐기, 피세닐기, 페릴레닐기, 클로로페릴레닐기, 펜타페닐기, 펜타세닐기, 테트라페닐레닐기, 헥사페닐기, 헥사세닐기, 루비세닐기, 코로네닐기, 트리나프틸레닐기, 헵타페닐기, 헵타세닐기, 플루오레닐기, 피란트레닐기, 오바레닐기, 카르바졸릴기, 디벤조퓨라닐기, 디벤조티오페닐기, 티오페닐기, 인돌일기, 푸리닐기, 벤즈이미다졸일기, 퀴놀리닐기, 벤조티오페닐기, 파라티아지닐기, 피롤일기, 피라졸릴기, 이미다졸릴기, 이미다졸리닐기, 옥사졸릴기, 티아졸릴기, 트리아졸릴기, 테트라졸일기, 옥사디아졸릴기, 피리디닐기, 피리다지닐기, 피리미디닐기, 피라지닐기, 티안트레닐기(thianthrenyl), 사이클로펜틸기, 사이클로헥실기, 옥시라닐기, 피롤리디닐기, 피라졸리디닐기, 이미다졸리디닐기, 피페리디닐기, 피페라지닐기, 모르폴리닐기, 디(C6-C50아릴)아미노기, 실레인기 및 이들의 유도체로 이루어진 군으로부터 선택된 것을 특징으로 하는 염료 감응 태양 전지용 루테늄계 염료.The method of claim 1,
R1 is a phenyl group, tolyl group, biphenyl group, pentarenyl group, indenyl group, naphthyl group, biphenylenyl group, anthracenyl group, benzoanthracenyl group, azurenyl group, heptarenyl group, acenaphthylyl group, phenareren Neyl group, methyl anthryl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, pisenyl group, peryllenyl group, chloroperylenyl group, pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexaphenyl group , Hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptasenyl group, fluorenyl group, pyrantrenyl group, ovarenyl group, carbazolyl group, dibenzofuranyl group, dibenzothio Phenyl group, thiophenyl group, indolyl group, furinyl group, benzimidazolyl group, quinolinyl group, benzothiophenyl group, parathiazinyl group, pyrroylyl group, pyrazolyl group, imidazolyl group, imidazolinyl group, oxazolyl group, Thiazolyl group, triazolyl group, tetrazolyl group, oxadiazole Group, pyridinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, thianthrenyl group, thianthrenyl group, cyclopentyl group, cyclohexyl group, oxiranyl group, pyrrolidinyl group, pyrazolidinyl group, imida A ruthenium-based dye for a dye-sensitized solar cell, which is selected from the group consisting of zolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, di (C6-C50 aryl) amino group, silane group and derivatives thereof.
상기 화학식 S에서 A는 하기 화학식 1 내지 64로 표시되는 것을 특징으로 하는 염료 감응 태양 전지용 루테늄계 염료:
In the chemical formula S, A is a ruthenium dye for dye-sensitized solar cells, characterized in that represented by the following Chemical Formulas 1 to 64:
상기 제1전극의 어느 한 일면에 형성된 광 흡수층;
상기 광 흡수층이 형성된 제1전극에 대향하여 배치되는 제2전극; 및
상기 제1전극과 제2전극 사이에 위치하는 전해질을 포함하며,
상기 광 흡수층은 반도체 미립자, 및 상기 제4항에 따른 염료를 포함하는 것인 염료 감응 태양 전지.A first electrode comprising a substrate having conductivity and light transmission;
A light absorbing layer formed on one surface of the first electrode;
A second electrode disposed to face the first electrode on which the light absorption layer is formed; And
An electrolyte located between the first electrode and the second electrode,
The light-sensing layer is a dye-sensitized solar cell comprising a semiconductor fine particle, and the dye according to claim 4.
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