JP6362208B2 - Organic dye complex and method for producing the same - Google Patents
Organic dye complex and method for producing the same Download PDFInfo
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- JP6362208B2 JP6362208B2 JP2013224496A JP2013224496A JP6362208B2 JP 6362208 B2 JP6362208 B2 JP 6362208B2 JP 2013224496 A JP2013224496 A JP 2013224496A JP 2013224496 A JP2013224496 A JP 2013224496A JP 6362208 B2 JP6362208 B2 JP 6362208B2
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- Prior art keywords
- porphyrin
- substituted
- complex
- added
- tri
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000004033 porphyrin derivatives Chemical class 0.000 claims description 68
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 52
- 125000004429 atom Chemical group 0.000 claims description 24
- 239000004065 semiconductor Substances 0.000 claims description 23
- 125000001072 heteroaryl group Chemical group 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 16
- 150000004032 porphyrins Chemical class 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 125000000962 organic group Chemical group 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000002165 photosensitisation Effects 0.000 claims description 4
- 239000003504 photosensitizing agent Substances 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 229910052752 metalloid Inorganic materials 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 154
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 96
- -1 porphyrin compound Chemical class 0.000 description 77
- 230000015572 biosynthetic process Effects 0.000 description 69
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 68
- 239000000975 dye Substances 0.000 description 67
- 238000003786 synthesis reaction Methods 0.000 description 67
- 238000006243 chemical reaction Methods 0.000 description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 66
- 239000000243 solution Substances 0.000 description 59
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- 239000000741 silica gel Substances 0.000 description 52
- 229910002027 silica gel Inorganic materials 0.000 description 52
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 48
- 239000000203 mixture Substances 0.000 description 46
- 239000000047 product Substances 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 239000012043 crude product Substances 0.000 description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- 239000002904 solvent Substances 0.000 description 31
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 22
- 238000000862 absorption spectrum Methods 0.000 description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 22
- 239000012074 organic phase Substances 0.000 description 22
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 20
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 17
- 239000010410 layer Substances 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 229910044991 metal oxide Inorganic materials 0.000 description 15
- 150000004706 metal oxides Chemical class 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 13
- 230000002378 acidificating effect Effects 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 11
- 235000019253 formic acid Nutrition 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 229910015900 BF3 Inorganic materials 0.000 description 10
- BIAUAWMKTMTGIY-UHFFFAOYSA-N C(CCCCC)C1=CC=C(S1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2C2=CC=C(C=C2)C(=O)OC Chemical compound C(CCCCC)C1=CC=C(S1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2C2=CC=C(C=C2)C(=O)OC BIAUAWMKTMTGIY-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- MNHWRUCVFATHDL-UHFFFAOYSA-N 2-methylterephthalaldehyde Chemical compound CC1=CC(C=O)=CC=C1C=O MNHWRUCVFATHDL-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 7
- 229910001887 tin oxide Inorganic materials 0.000 description 7
- VWCAHBARARIQLV-UHFFFAOYSA-N 5-hexylthiophene-2-carbaldehyde Chemical compound CCCCCCC1=CC=C(C=O)S1 VWCAHBARARIQLV-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000012860 organic pigment 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
- 238000003756 stirring Methods 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- FRLGLIZOVAOJPU-UHFFFAOYSA-N 2-(4-hexylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound C1=CC(CCCCCC)=CC=C1B1OC(C)(C)C(C)(C)O1 FRLGLIZOVAOJPU-UHFFFAOYSA-N 0.000 description 4
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000010408 film 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
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 3
- DPFMUYPHQAGJFO-UHFFFAOYSA-N 4-(5-hexylthiophen-2-yl)benzaldehyde Chemical compound CCCCCCC1=CC=C(S1)C2=CC=C(C=C2)C=O DPFMUYPHQAGJFO-UHFFFAOYSA-N 0.000 description 3
- WVAPYJUSKYIJEX-UHFFFAOYSA-N 5-(3,6-ditert-butylcarbazol-9-yl)thiophene-2-carbaldehyde Chemical compound CC(C)(C)c1ccc2n(-c3ccc(C=O)s3)c3ccc(cc3c2c1)C(C)(C)C WVAPYJUSKYIJEX-UHFFFAOYSA-N 0.000 description 3
- NTHMTYNJFSUBMF-UHFFFAOYSA-N 5-(5-bromothiophen-2-yl)thiophene-2-carbaldehyde Chemical compound S1C(Br)=CC=C1C1=CC=C(C=O)S1 NTHMTYNJFSUBMF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OTZKZBHRAREFKP-UHFFFAOYSA-N C(CCCCC)C1=CC=C(C=C1)C1=CC=C(S1)C1=CC=C(S1)C=O Chemical compound C(CCCCC)C1=CC=C(C=C1)C1=CC=C(S1)C1=CC=C(S1)C=O OTZKZBHRAREFKP-UHFFFAOYSA-N 0.000 description 3
- ISRLDSGZPGDDQH-UHFFFAOYSA-N C(CCCCC)C1=CC=C(C=C1)C1=CC=C(S1)C=O Chemical compound C(CCCCC)C1=CC=C(C=C1)C1=CC=C(S1)C=O ISRLDSGZPGDDQH-UHFFFAOYSA-N 0.000 description 3
- MBVMOYGQFQTRCK-UHFFFAOYSA-N C1=CC(OC)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(OC)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 MBVMOYGQFQTRCK-UHFFFAOYSA-N 0.000 description 3
- IARNVKSBRPYBMQ-UHFFFAOYSA-N COC(=O)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 Chemical compound COC(=O)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 IARNVKSBRPYBMQ-UHFFFAOYSA-N 0.000 description 3
- IBOCDLDLUYAGKR-UHFFFAOYSA-N COC(C(C=C1)=CC=C1C1=C(C(C#CC2=CC=CC=C2)=C(C=C2)N=C2C=C(C=C2)NC2=CC(C=C2)=NC2=C2)NC2=C1)=O Chemical compound COC(C(C=C1)=CC=C1C1=C(C(C#CC2=CC=CC=C2)=C(C=C2)N=C2C=C(C=C2)NC2=CC(C=C2)=NC2=C2)NC2=C1)=O IBOCDLDLUYAGKR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- DHTJXVAXIYPGJT-UHFFFAOYSA-N [Zn+2].C(CCCCC)C1=CC=C(S1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2C2=CC=C(C=C2)C(=O)OC Chemical compound [Zn+2].C(CCCCC)C1=CC=C(S1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2C2=CC=C(C=C2)C(=O)OC DHTJXVAXIYPGJT-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 3
- QVWFJWHNMQTCAV-UHFFFAOYSA-N methyl 4-[3-[5-(4-hexylphenyl)thiophen-2-yl]-21,23-dihydroporphyrin-5-yl]benzoate Chemical compound C(CCCCC)C1=CC=C(C=C1)C1=CC=C(S1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2C1=CC=C(C=C1)C(=O)OC QVWFJWHNMQTCAV-UHFFFAOYSA-N 0.000 description 3
- AEIGICUIJCFSTI-UHFFFAOYSA-N methyl 4-[3-[5-[5-(4-hexylphenyl)thiophen-2-yl]thiophen-2-yl]-21,23-dihydroporphyrin-5-yl]benzoate Chemical compound C(CCCCC)C1=CC=C(C=C1)C1=CC=C(S1)C1=CC=C(S1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2C1=CC=C(C=C1)C(=O)OC AEIGICUIJCFSTI-UHFFFAOYSA-N 0.000 description 3
- APNKWEPRZUSZCJ-UHFFFAOYSA-N methyl 5-formylthiophene-2-carboxylate Chemical compound COC(=O)C1=CC=C(C=O)S1 APNKWEPRZUSZCJ-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- SRIJSZQFAMLVQV-UHFFFAOYSA-N 4,5-dichlorobenzene-1,2-dicarbonitrile Chemical compound ClC1=CC(C#N)=C(C#N)C=C1Cl SRIJSZQFAMLVQV-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- PJOJZHHAECOAFH-UHFFFAOYSA-N 5,10,15,20-tetrakis(4-methoxyphenyl)-21,23-dihydroporphyrin Chemical compound COc1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(OC)cc2)c2ccc([nH]2)c(-c2ccc(OC)cc2)c2ccc(n2)c(-c2ccc(OC)cc2)c2ccc1[nH]2 PJOJZHHAECOAFH-UHFFFAOYSA-N 0.000 description 2
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- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- OOHQHYJZUSXMFD-UHFFFAOYSA-N 4-iodobenzene-1,2-dicarbonitrile Chemical compound IC1=CC=C(C#N)C(C#N)=C1 OOHQHYJZUSXMFD-UHFFFAOYSA-N 0.000 description 1
- GFBVUFQNHLUCPX-UHFFFAOYSA-N 5-bromothiophene-2-carbaldehyde Chemical compound BrC1=CC=C(C=O)S1 GFBVUFQNHLUCPX-UHFFFAOYSA-N 0.000 description 1
- VFEAMMGYJFFXKV-UHFFFAOYSA-N 5-formylthiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=C(C=O)S1 VFEAMMGYJFFXKV-UHFFFAOYSA-N 0.000 description 1
- FYBWRAXKYXTOQC-UHFFFAOYSA-N 5-thiophen-2-ylthiophene-2-carbaldehyde Chemical compound S1C(C=O)=CC=C1C1=CC=CS1 FYBWRAXKYXTOQC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- WPPYGBXZVQYDKJ-UHFFFAOYSA-N [Zn].C(CCCCC)C1=CC=C(S1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical compound [Zn].C(CCCCC)C1=CC=C(S1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 WPPYGBXZVQYDKJ-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- URINKTWOCVLGGR-UHFFFAOYSA-N methyl 4-(4-formylphenyl)benzoate Chemical compound C1=CC(C(=O)OC)=CC=C1C1=CC=C(C=O)C=C1 URINKTWOCVLGGR-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- OLBCVFGFOZPWHH-UHFFFAOYSA-N propofol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O OLBCVFGFOZPWHH-UHFFFAOYSA-N 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C09B47/00—Porphines; Azaporphines
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0035—Mixtures of phthalocyanines
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Description
本発明は、フタロシアニン誘導体とポルフィリン誘導体とからなる新規有機複合体に関する。また本発明は、該複合体を利用した機能性材料に関し、詳細には該複合体を含む金属酸化物半導体電極および該電極を含む色素増感太陽電池に関する。 The present invention relates to a novel organic complex comprising a phthalocyanine derivative and a porphyrin derivative. The present invention also relates to a functional material using the composite, and more particularly to a metal oxide semiconductor electrode including the composite and a dye-sensitized solar cell including the electrode.
有機色素は、その骨格や置換基、配位金属等を変更することにより、その吸収波長および発光波長を移動させることができることから、所望の吸収/発光波長を有する構造の設計が数多く検討されている。 Since organic dyes can shift their absorption and emission wavelengths by changing their skeleton, substituents, coordination metals, etc., many designs of structures having desired absorption / emission wavelengths have been studied. Yes.
このような所望の吸収/発光波長を有する有機色素は電子デバイスをはじめとする種々の分野で有用であり、例えば、発光素子分野では有機色素の設計により、色の異なる発光素子を提供することができる。 Such organic dyes having a desired absorption / emission wavelength are useful in various fields including electronic devices. For example, in the light emitting element field, it is possible to provide light emitting elements having different colors by designing organic dyes. it can.
また、有機色素増感太陽電池分野では、より効率よく太陽光エネルギーを利用できるように、より広域の波長を吸収できる有機色素が好ましい。 In the field of organic dye-sensitized solar cells, organic dyes that can absorb a wider range of wavelengths are preferred so that solar energy can be used more efficiently.
従来、色素増感太陽電池に用いられてきた色素は、大部分が赤色を示すポリピリジンRu系色素であった(特許文献1〜4)。近年、ポリピリジン系以外の骨格を有する色素の開発が行われており、例えば、ポルフィリン系色素(特許文献5および6)やフタロシアニン系色素の利用なども試みられている(特許文献7および8)。 Conventionally, most of the dyes that have been used in dye-sensitized solar cells are polypyridine Ru-based dyes that exhibit red color (Patent Documents 1 to 4). In recent years, dyes having a skeleton other than polypyridine have been developed, and for example, use of porphyrin dyes (Patent Documents 5 and 6) and phthalocyanine dyes has been attempted (Patent Documents 7 and 8).
さらに、複数の色素を用いた色素増感太陽電池の研究も行われている(例えば、非特許文献1等参照)。しかしながら、このような方法では、それぞれ単独の色素の吸収領域しか利用することができなかった。 Furthermore, research on dye-sensitized solar cells using a plurality of dyes has also been conducted (see, for example, Non-Patent Document 1). However, in such a method, only a single dye absorption region can be used.
さらに、複数の有機色素を組み合わせる場合、色素同士の相性も重要であり、波長特性に基づき選択された組み合わせであっても、変換効率を向上することができない場合も多い。特に、色素増感太陽電池に利用するのに好ましい近赤外領域の光を効率よく利用可能な色素は少なく、色素の組み合わせも限られていた。 Furthermore, when combining a plurality of organic dyes, the compatibility between the dyes is also important, and in many cases, the conversion efficiency cannot be improved even with a combination selected based on wavelength characteristics. In particular, there are few dyes that can efficiently use light in the near infrared region, which is preferable for use in dye-sensitized solar cells, and combinations of dyes are limited.
本発明は、より広域の吸収波長を有する、特に近赤外領域においてより広域の吸収波長を有する有機色素複合体を提供することを目的とする。さらに、該複合体の機能性材料への利用を目的とする。詳細には、該複合体を用いた電子デバイス、さらに詳細には、該会合体を酸化物半導体上に吸着させた金属酸化物半導体電極、および該酸化物半導体電極を用いた色素増感太陽電池を提供することを目的とする。 An object of the present invention is to provide an organic dye complex having a broader absorption wavelength, particularly a broader absorption wavelength in the near infrared region. Furthermore, it aims at utilization to the functional material of this composite_body | complex. More specifically, an electronic device using the composite, more specifically, a metal oxide semiconductor electrode in which the aggregate is adsorbed on an oxide semiconductor, and a dye-sensitized solar cell using the oxide semiconductor electrode The purpose is to provide.
本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、下記式(1)の構造を有するフタロシアニン誘導体と式(2)の構造を有するポルフィリン誘導体との複合体が、これらの構成分子単独の吸収波長の和とは異なる新たな吸収波長を有することを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor has found that a complex of a phthalocyanine derivative having the structure of the following formula (1) and a porphyrin derivative having the structure of the following formula (2) It has been found that it has a new absorption wavelength different from the sum of the single absorption wavelengths, and has completed the present invention.
(式中、R1〜R8はそれぞれ独立して、水素原子、置換もしくは無置換のアリールまたは置換もしくは無置換のヘテロアリールであり、または隣りあったRnおよびRn+1が共通する一の置換もしくは無置換のアリールまたは置換もしくは無置換のヘテロアリールを形成してもよく、
X1〜X8はそれぞれ独立して、O、S、CH2から選択され、n1〜n8はそれぞれ独立して0または1であり、
M1はフタロシアニンと結合しうる任意の少なくとも1つの原子または原子団を表す)
(Wherein R 1 to R 8 are each independently a hydrogen atom, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, or a common substitution of adjacent R n and R n + 1. Or may form an unsubstituted aryl or a substituted or unsubstituted heteroaryl,
X 1 to X 8 are each independently selected from O, S, and CH 2 , and n 1 to n 8 are each independently 0 or 1,
M 1 represents any at least one atom or atomic group capable of binding to phthalocyanine)
(式中、A、B、C、およびDはそれぞれ独立して水素原子、ハロゲン原子、または1価の有機基を示し、前記A〜Dのうち少なくとも2つは置換もしくは無置換のアリールまたは置換もしくは無置換のヘテロアリールであり、
M2はポルフィリンと結合しうる任意の少なくとも1つの原子または原子団を表す)
(In the formula, A, B, C, and D each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, and at least two of the A to D are substituted or unsubstituted aryl or substituted. Or unsubstituted heteroaryl,
M 2 represents any at least one atom or atomic group capable of binding to porphyrin)
本発明は、各構成分子単独の吸収波長の単なる和とは異なる、より広域の吸収波長を有する新規有機色素複合体を提供できる。このような有機色素複合体は機能性材料として利用することができ、例えば、より広域の太陽光エネルギーを吸収することにより、これを用いた色素増感太陽電池の効率を向上させることができる。 The present invention can provide a novel organic dye complex having a broader range of absorption wavelengths that is different from the mere sum of the absorption wavelengths of each constituent molecule alone. Such an organic dye complex can be used as a functional material. For example, by absorbing solar energy in a wider area, the efficiency of a dye-sensitized solar cell using the organic dye complex can be improved.
本発明は、フタロシアニン誘導体とポルフィリン誘導体とからなる新規有機色素複合体に関する。また本発明は、該複合体を利用した機能性材料に関し、詳細には、該複合体を用いた電子デバイス、さらに詳細には該複合体を含む金属酸化物半導体電極および該電極を含む色素増感太陽電池に関する。 The present invention relates to a novel organic dye complex comprising a phthalocyanine derivative and a porphyrin derivative. The present invention also relates to a functional material using the composite, and more particularly, to an electronic device using the composite, and more particularly to a metal oxide semiconductor electrode including the composite and a dye sensitizer including the electrode. It relates to a solar cell.
以下、本発明の好適な実施形態について詳細に説明する。なお、以下に示す実施形態は、本発明の単なる一例であって、当業者であれば、適宜設計変更可能である。 Hereinafter, preferred embodiments of the present invention will be described in detail. The following embodiment is merely an example of the present invention, and those skilled in the art can change the design as appropriate.
有機色素複合体
本発明の有機色素複合体は、式(1)の構造を有するフタロシアニン誘導体と式(2)の構造を有するポルフィリン誘導体とからなる。
Organic dye complex The organic dye complex of the present invention comprises a phthalocyanine derivative having the structure of formula (1) and a porphyrin derivative having the structure of formula (2).
(フタロシアニン誘導体)
本発明のフタロシアニン誘導体は、下記式(1)の構造を有する化合物およびその塩である。
(Phthalocyanine derivatives)
The phthalocyanine derivative of the present invention is a compound having the structure of the following formula (1) and a salt thereof.
上記の一般式(1)において、R1〜R8はそれぞれ独立して、水素原子、置換もしくは無置換のアリールまたは置換もしくは無置換のヘテロアリールであり、または隣りあったRnおよびRn+1が共通する一の置換もしくは無置換のアリールまたは置換もしくは無置換のヘテロアリールを形成してもよい。好ましくは、上記R1〜R8のうち、4つ以上が同時に水素原子とはならない。 In the general formula (1), R 1 to R 8 are each independently a hydrogen atom, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, or adjacent R n and R n + 1 are One common substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl may be formed. Preferably, four or more of the above R 1 to R 8 do not become hydrogen atoms at the same time.
前記式(1)を構成するアリールは、これらに限定されないが、フェニレン環およびナフタレン環を含み、前記式(1)を構成するへテロアリールとしては、チオフェン環、ピロール環、フラン環、イミダゾール環、ピラゾール環、オキサゾール環、イソオキサゾール環、チアゾール環、イソチアゾール環などの5員環、ピリジン環、ピリミジン環、ピリダジン環、ピラジン環、1,2,3−トリアジン環などの6員環を含む。 The aryl constituting the formula (1) includes, but is not limited to, a phenylene ring and a naphthalene ring. The heteroaryl constituting the formula (1) includes a thiophene ring, a pyrrole ring, a furan ring, an imidazole ring, 5-membered rings such as a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring and an isothiazole ring, and a 6-membered ring such as a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring and a 1,2,3-triazine ring are included.
前記式(1)を構成するアリールまたはヘテロアリールは、メチル基、エチル基などの炭素数1〜6のアルキル基;ベンジル基などのアラルキル基;ビニル基などのアルケニル基;シアノ基;アミノ基;アシル基;メトキシ基、エトキシ基などの炭素数1〜6のアルコキシ基;カルボニル基;メトキシカルボニル基、エトキシカルボニル基などの炭素数1〜6のアルコキシカルボニル基;フェノキシ基、ベンジルオキシ基などのアリールオキシ基;ジエチルアミノ基、イソプロピルアミノ基などのジアルキルアミノ基;ジベンジルアミノ基、ジフェネチルアミノ基などのジアラルキルアミノ基;ニトロ基;トリフルオロメチル基などのα−ハロアルキル基;ハロゲン;水酸基;スルホ基により置換されてもよい。 The aryl or heteroaryl constituting the formula (1) is an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; an aralkyl group such as a benzyl group; an alkenyl group such as a vinyl group; a cyano group; Acyl group; alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; carbonyl group; alkoxycarbonyl group having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; aryl such as phenoxy group and benzyloxy group Oxy group; Dialkylamino group such as diethylamino group and isopropylamino group; Diaralkylamino group such as dibenzylamino group and diphenethylamino group; Nitro group; α-haloalkyl group such as trifluoromethyl group; Halogen; Hydroxyl group; It may be substituted by a group.
上記一般式(1)において、X1〜X8はそれぞれ独立して、O、S、CH2から選択され、n1〜n8はそれぞれ独立して0または1である。好ましくはX1〜X8はOである。また好ましくは、n1〜n8のうち、少なくとも5つが1である。 In the general formula (1), X 1 to X 8 are each independently selected from O, S, and CH 2 , and n 1 to n 8 are each independently 0 or 1. X 1 to X 8 are preferably O. Preferably, at least five of n 1 to n 8 are 1.
上記一般式(1)において、M1はフタロシアニンと結合しうる任意の少なくとも1つの原子または原子団を表す。M1は中心原子単体であってもよく、中心原子が他の物質と結合した中心原子団であってもよい。 In the general formula (1), M 1 represents any at least one atom or atomic group capable of binding to phthalocyanine. M 1 may be a single central atom or a central atomic group in which the central atom is bonded to another substance.
本発明の式(1)のフタロシアニン誘導体において、中心原子は1個でもよく、2個以上であってもよい。中心原子が2個以上であるものの具体例としては、無金属フタロシアニン誘導体が挙げられる。無金属フタロシアニン誘導体においては、窒素に結合した2個の水素がそれぞれ中心原子となる。 In the phthalocyanine derivative of the formula (1) of the present invention, the central atom may be one or two or more. Specific examples of those having two or more central atoms include metal-free phthalocyanine derivatives. In the metal-free phthalocyanine derivative, two hydrogen atoms bonded to nitrogen are each a central atom.
また、中心原子団を中心原子とともに構成する他の物質は任意である。例えば、これらに限定されないが、他の物質と結合した中心原子団M1は、酸化物、水酸化物、ハロゲン化物であってもよい。 Moreover, the other substance which comprises a central atomic group with a central atom is arbitrary. For example, but not limited thereto, the central atomic group M 1 bonded to another substance may be an oxide, a hydroxide, or a halide.
また、水素原子以外のM1は、典型金属元素、半金属元素、遷移金属元素であってもよい。M1が水素原子以外の中心原子単体である場合、中心元素M1は、亜鉛、アルミニウム、マグネシウム、銅、ニッケル、コバルト、ルテニウム、ロジウム、オスミニウム、鉛、および錫からなる金属元素の群またはケイ素から選択される。好ましくは、亜鉛および銅である。 Further, M 1 other than a hydrogen atom may be a typical metal element, a metalloid element, or a transition metal element. When M 1 is a single central atom other than a hydrogen atom, the central element M 1 is a group of metal elements composed of zinc, aluminum, magnesium, copper, nickel, cobalt, ruthenium, rhodium, osmium, lead, and tin, or silicon Selected from. Zinc and copper are preferred.
式(1)で表されるフタロシアニン誘導体は、例えば、以下の化合物A〜Dおよびその塩を含む。なお本発明のフタロシアニン誘導体の製造方法に関しては、後述する実施例において具体的に詳述する。 The phthalocyanine derivative represented by the formula (1) includes, for example, the following compounds A to D and salts thereof. In addition, about the manufacturing method of the phthalocyanine derivative of this invention, it explains in full detail in the Example mentioned later.
(ポルフィリン誘導体)
本発明のポルフィリン誘導体は、下記式(2)を有する化合物およびその塩である。
(Porphyrin derivative)
The porphyrin derivative of the present invention is a compound having the following formula (2) and a salt thereof.
上記の一般式(2)において、A、B、C、およびDはそれぞれ独立して水素原子、ハロゲン原子、または1価の有機基を示し、前記A〜Dのうち少なくとも2つは置換もしくは無置換のアリール基または置換もしくは無置換のヘテロアリール基である。 In the general formula (2), A, B, C, and D each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group, and at least two of the A to D are substituted or unsubstituted. A substituted aryl group or a substituted or unsubstituted heteroaryl group.
1価の有機基の具体例としては、これらに限定されないが、メチル基、エチル基などの炭素数1〜6のアルキル基;ベンジル基などのアラルキル基;ビニル基などのアルケニル基;フェニルエチニル基などのアルキニル基;シアノ基;アミノ基;アシル基;メトキシ基、エトキシ基などの炭素数1〜6のアルコキシ基;カルボニル基;メトキシカルボニル基、エトキシカルボニル基などの炭素数1〜6のアルコキシカルボニル基;フェノキシ基、ベンジルオキシ基などのアリールオキシ基;ジエチルアミノ基、イソプロピルアミノ基などのジアルキルアミノ基;ジベンジルアミノ基、ジフェネチルアミノ基などのジアラルキルアミノ基;ニトロ基;トリフルオロメチル基などのα−ハロアルキル基;水酸基;スルホ基;置換もしくは無置換のフェニレン環およびナフタレン環などのアリール基;チオフェン環、ピロール環、フラン環、イミダゾール環、ピラゾール環、オキサゾール環、イソオキサゾール環、チアゾール環、イソチアゾール環などの5員環、およびピリジン環、ピリミジン環、ピリダジン環、ピラジン環、1,2,3−トリアジン環などの6員環を含む置換もしくは無置換のヘテロアリール基を含む。前記式(2)を構成するアリールまたはヘテロアリールは、1または複数のハロゲンまたは1価の有機基により、さらに置換されていてもよい。 Specific examples of the monovalent organic group include, but are not limited to, an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an aralkyl group such as a benzyl group; an alkenyl group such as a vinyl group; a phenylethynyl group. Alkynyl group such as cyano group; amino group; acyl group; alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; carbonyl group; alkoxycarbonyl having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group Groups; aryloxy groups such as phenoxy group and benzyloxy group; dialkylamino groups such as diethylamino group and isopropylamino group; diaralkylamino groups such as dibenzylamino group and diphenethylamino group; nitro group; trifluoromethyl group and the like Α-haloalkyl group of; hydroxyl group; sulfo group; substituted or unsubstituted Aryl groups such as enylene ring and naphthalene ring; 5-membered rings such as thiophene ring, pyrrole ring, furan ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, and pyridine ring, pyrimidine ring A substituted or unsubstituted heteroaryl group containing a 6-membered ring such as a pyridazine ring, a pyrazine ring, or a 1,2,3-triazine ring. The aryl or heteroaryl constituting the formula (2) may be further substituted with one or more halogens or a monovalent organic group.
また、上記一般式(2)において、M2はポルフィリンと結合しうる任意の少なくとも1つの原子または原子団を表す。M2は中心原子単体であってもよく、中心原子が他の物質と結合した中心原子団であってもよい。 In the general formula (2), M 2 represents any of the at least one atom or atomic group capable of binding to porphyrin. M 2 may be a single central atom or a central atomic group in which the central atom is bonded to another substance.
本発明の式(2)のポルフィリン誘導体において、中心原子は1個でもよく、2個以上であってもよい。中心原子が2個以上であるものの具体例としては、無金属ポルフィリン誘導体が挙げられる。無金属ポルフィリン誘導体においては、窒素に結合した2個の水素がそれぞれ中心原子となる。 In the porphyrin derivative of the formula (2) of the present invention, the number of central atoms may be one, or two or more. Specific examples of those having 2 or more central atoms include metal-free porphyrin derivatives. In the metal-free porphyrin derivative, two hydrogen atoms bonded to nitrogen are each a central atom.
また、中心原子団を中心原子とともに構成する他の物質は任意である。例えば、これらに限定されないが、他の物質と結合した中心原子団M2は、酸化物、水酸化物、ハロゲン化物であってもよい。 Moreover, the other substance which comprises a central atomic group with a central atom is arbitrary. For example, but not limited thereto, the central atomic group M 2 bonded to another substance may be an oxide, a hydroxide, or a halide.
また、水素原子以外のM2は、典型金属元素、半金属元素、遷移金属元素であってもよい。M2が水素原子以外の中心原子単体である場合、中心元素M2は、亜鉛、アルミニウム、マグネシウム、銅、ニッケル、コバルト、ルテニウム、ロジウム、オスミニウム、鉛、および錫からなる金属元素の群またはケイ素から選択される。好ましくは、亜鉛、銅、鉄、およびコバルトである。 Further, M 2 other than a hydrogen atom may be a typical metal element, a metalloid element, or a transition metal element. When M 2 is a single central atom other than a hydrogen atom, the central element M 2 is a group of metal elements consisting of zinc, aluminum, magnesium, copper, nickel, cobalt, ruthenium, rhodium, osmium, lead, and tin, or silicon Selected from. Zinc, copper, iron, and cobalt are preferable.
式(2)で表されるポルフィリン誘導体は、例えば、表1で示される以下の化合物P1〜P15およびそれらの塩を含む。なお本発明のポルフィリン誘導体の製造方法に関しては、後述する実施例において具体的に詳述する。 The porphyrin derivative represented by the formula (2) includes, for example, the following compounds P1 to P15 shown in Table 1 and salts thereof. In addition, regarding the manufacturing method of the porphyrin derivative of this invention, it explains in full detail in the Example mentioned later.
(有機色素複合体の調製)
本発明の有機色素複合体は、上記式(1)を有するフタロシアニン誘導体と上記式(2)を有するポルフィリン誘導体とを溶媒中で混合することにより形成することができる。具体的には、これらに限定されないが、(i)該フタロシアニン誘導体溶液と該ポルフィリン誘導体溶液を混合することにより、(ii)一方の化合物を溶解させた溶液に、もう一方の化合物を溶解させることにより、または(iii)該フタロシアニン誘導体と該ポルフィリン誘導体とを固形状態で混合し、溶媒で溶解することにより、本発明の有機色素複合体を形成してもよい。
(Preparation of organic dye complex)
The organic dye complex of the present invention can be formed by mixing a phthalocyanine derivative having the above formula (1) and a porphyrin derivative having the above formula (2) in a solvent. Specifically, but not limited thereto, (i) by mixing the phthalocyanine derivative solution and the porphyrin derivative solution, (ii) dissolving the other compound in a solution in which one compound is dissolved. Or (iii) The organic dye complex of the present invention may be formed by mixing the phthalocyanine derivative and the porphyrin derivative in a solid state and dissolving in a solvent.
本発明の有機色素複合体は、上記式(1)のフタロシアニン誘導体と上記式(2)のポルフィリン誘導体との会合体を含む。 The organic dye complex of the present invention includes an association product of the phthalocyanine derivative of the above formula (1) and the porphyrin derivative of the above formula (2).
該会合体は、混合されたフタロシアニン誘導体およびポルフィリン誘導体のいずれとも異なる新たな吸収スペクトルを有する。図1aは、(i)フタロシアニン誘導体A、(ii)ポルフィリン誘導体P1、および(iii)これらの有機色素複合体(A+P1)を二酸化チタン上に吸着させた際の紫外・可視吸収スペクトルを示す。図1bはこれらの化合物のエタノール溶液(5μmol/L)中での紫外・可視吸収スペクトルをそれぞれ示す。 The aggregate has a new absorption spectrum different from any of the mixed phthalocyanine derivative and porphyrin derivative. FIG. 1a shows an ultraviolet / visible absorption spectrum when (i) phthalocyanine derivative A, (ii) porphyrin derivative P1, and (iii) these organic dye complexes (A + P1) are adsorbed on titanium dioxide. FIG. 1b shows the ultraviolet and visible absorption spectra of these compounds in an ethanol solution (5 μmol / L), respectively.
有機色素複合体を形成するために用いることのできる溶媒は、混合するフタロシアニン誘導体およびポルフィリン誘導体が溶解するものであればよい。具体的には、これらに限定されないが、ペンタン、ヘキサン、オクタン、ノナン、メチルシクロヘキサン、エチルシクロヘキサン等の鎖状および環状飽和脂肪族系溶媒;トルエン、キシレン、ナフタレン、テトラヒドロナフタレン、メチルナフタレン、ジフェニルメタン、アニソール等の芳香族系溶媒;クロロベンゼン、ジクロロベンゼン、クロロナフタレン等のハロゲン化芳香族系溶媒;メタノール、エタノール、イソプロパノール、n−ブタノール、ベンジルアルコール等のアルコール系溶媒;エチレングリコール、グリセリン、ポリエチレングリコール等の脂肪族多価アルコール類;アセトン、シクロヘキサノン、メチルエチルケトン等の鎖状および環状ケトン系溶媒;ギ酸メチル、酢酸エチル、酢酸n−ブチル等のエステル系溶媒;塩化メチレン、クロロホルム、1,2−ジクロロエタン等のハロゲン化炭化水素系溶媒;ジエチルエーテル、ジメトキシエタン、テトラヒドロフラン、1,4−ジオキサン、1,3−ジオキサリン、メチルセルソルブ、エチルセルソルブ、ブチルセルソルブ等の鎖状および環状エーテル系溶媒;ジメチルホルムアミド、N−メチル−2−ピロリドン、ジメチルスルホキシド、スルフォラン、1,3−ジメチル−2−イミダゾリノン、2−ブチロラクトン、ヘキサメチルリン酸トリアミド等の非プロトン性極性溶媒;n−ブチルアミン、イソプロパノールアミン、ジエチルアミン、トリエタノールアミン、エチレンジアミン、トリエチレンジアミン、トリエチルアミン等の含窒素化合物;およびこれらの混合物を含む。好ましくは、エタノール、クロロホルムである。 The solvent that can be used to form the organic dye complex may be any solvent that dissolves the phthalocyanine derivative and porphyrin derivative to be mixed. Specific examples include, but are not limited to, chain and cyclic saturated aliphatic solvents such as pentane, hexane, octane, nonane, methylcyclohexane, and ethylcyclohexane; toluene, xylene, naphthalene, tetrahydronaphthalene, methylnaphthalene, diphenylmethane, Aromatic solvents such as anisole; Halogenated aromatic solvents such as chlorobenzene, dichlorobenzene, chloronaphthalene; Alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, benzyl alcohol; Ethylene glycol, glycerin, polyethylene glycol, etc. Aliphatic and polyhydric alcohols; linear and cyclic ketone solvents such as acetone, cyclohexanone, and methyl ethyl ketone; ester solvents such as methyl formate, ethyl acetate, and n-butyl acetate; Halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1,2-dichloroethane; diethyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxaline, methyl cellosolve, ethyl cellosolve, butyl cellosolve Linear and cyclic ether solvents such as dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, 1,3-dimethyl-2-imidazolinone, 2-butyrolactone, hexamethylphosphoric acid triamide, etc. Polar solvents; nitrogen-containing compounds such as n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine, triethylenediamine, triethylamine; and mixtures thereof. Preferably, ethanol and chloroform are used.
該フタロシアニン誘導体およびポルフィリン誘導体の混合工程の作業温度は、下限は使用する溶媒の凝固点以上であり、上限は使用する溶媒の沸点以下である。具体的には、10℃以上、200℃以下が好ましい。 As for the working temperature of the mixing step of the phthalocyanine derivative and porphyrin derivative, the lower limit is equal to or higher than the freezing point of the solvent used, and the upper limit is equal to or lower than the boiling point of the solvent used. Specifically, it is preferably 10 ° C. or higher and 200 ° C. or lower.
本発明の有機色素複合体は、少なくともその一部において上記会合体が形成する濃度で混合される。具体的には、有機色素複合体の濃度として1μmol/L以上が好ましく、5μmol/L以上がより好ましい。形成された有機色素複合体は、溶媒を除去し、固体状態にしてもよい。 The organic pigment | dye complex of this invention is mixed in the density | concentration which the said aggregate forms in at least one part. Specifically, the concentration of the organic dye complex is preferably 1 μmol / L or more, and more preferably 5 μmol / L or more. The formed organic dye complex may be in a solid state by removing the solvent.
上記式(1)のフタロシアニン誘導体および上記式(2)のポルフィリン誘導体は、少なくとも一部が上記会合体を形成する比率で混合され、例えば、1:9〜9:1の比で混合することができる。 The phthalocyanine derivative of the above formula (1) and the porphyrin derivative of the above formula (2) are mixed at a ratio at least partially forming the above-mentioned aggregate, for example, mixed at a ratio of 1: 9 to 9: 1. it can.
機能性材料
本発明の有機色素複合体は、機能性材料として利用することができる。詳細には、該複合体を用いた電子デバイス、さらに詳細には、該複合体を酸化物半導体上に吸着させた金属酸化物半導体電極、および該酸化物半導体電極を用いた色素増感太陽電池に用いることができる。
Functional Material The organic dye complex of the present invention can be used as a functional material. More specifically, an electronic device using the composite, more specifically, a metal oxide semiconductor electrode in which the composite is adsorbed on an oxide semiconductor, and a dye-sensitized solar cell using the oxide semiconductor electrode Can be used.
(金属酸化物半導体電極)
本発明は、さらに該有機色素複合体を用いた金属酸化物半導体電極に関する。本発明の金属酸化物半導体電極は、上述した本発明の有機色素複合体を金属酸化物半導体で形成された電極の表面に吸着させたものである。この金属酸化物半導体電極は、好ましくは多孔質電極とする。これによって、前記電極の実質的な表面積を増大させることができ、前記電極への光増感色素の吸着量を増大させて、前記金属酸化物半導体電極を含む太陽電池の光電変換効率を増大させることができるようになる。
(Metal oxide semiconductor electrode)
The present invention further relates to a metal oxide semiconductor electrode using the organic dye complex. The metal oxide semiconductor electrode of the present invention is obtained by adsorbing the organic dye complex of the present invention described above on the surface of an electrode formed of a metal oxide semiconductor. This metal oxide semiconductor electrode is preferably a porous electrode. Accordingly, the substantial surface area of the electrode can be increased, the amount of photosensitizing dye adsorbed on the electrode can be increased, and the photoelectric conversion efficiency of the solar cell including the metal oxide semiconductor electrode can be increased. Will be able to.
本発明の金属酸化物半導体には、チタン、スズ、亜鉛、鉄、タングステン、ジルコニウム、ハフニウム、ストロンチウム、インジウム、セリウム、イットリウム、ランタン、バナジウム、ニオブ、もしくはタンタルの酸化物、またはチタン酸ストロンチウム、チタン酸カルシウム、チタン酸ナトリウム、チタン酸バリウム、もしくはニオブ酸カリウムなどのぺロブスカイト構造を有する化合物を用いることができる。 The metal oxide semiconductor of the present invention includes titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, or tantalum oxide, or strontium titanate, titanium. A compound having a perovskite structure such as calcium oxide, sodium titanate, barium titanate, or potassium niobate can be used.
該有機色素複合体を金属酸化物半導体薄膜上に吸着させる方法としては、任意の公知の方法を用いることができる。たとえば、二酸化チタン等の金属酸化物半導体薄膜を本発明の有機色素複合体溶液に所定の温度で浸漬する方法(ディップ法、ローラ法、エヤーナイフ法など)および、該有機色素複合体溶液を金属酸化物半導体層状面に塗布する方法(ワイヤーバー法、アプリケーション法、スピン法、スプレー法、オフセット印刷法、スクリーン印刷法など)を挙げることができる。 Any known method can be used as a method for adsorbing the organic dye complex on the metal oxide semiconductor thin film. For example, a method of immersing a metal oxide semiconductor thin film such as titanium dioxide in the organic dye complex solution of the present invention at a predetermined temperature (dip method, roller method, air knife method, etc.), and the organic dye complex solution is oxidized by metal Examples thereof include a method of applying to a semiconductor layered surface (wire bar method, application method, spin method, spray method, offset printing method, screen printing method, etc.).
(色素増感太陽電池)
本発明はさらに、透明電極1、上記金属酸化物半導体電極2、電解質3、および対電極4を含む色素増感太陽電池に関する(図2参照)。
(Dye-sensitized solar cell)
The present invention further relates to a dye-sensitized solar cell including the transparent electrode 1, the metal oxide semiconductor electrode 2, the electrolyte 3, and the counter electrode 4 (see FIG. 2).
透明電極1は、透明基板上に透明導電層を形成して構成される(図示せず)。透明基板は、汎用のガラス基板、石英基板、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、およびポリエチレンなどの透明プラスチック基板を用いることができる。透明導電層は、酸化スズ、フッ素ドープ酸化スズ、ITO、ATO、酸化亜鉛、アルミドープ酸化亜鉛、またはこれらの表面に酸化スズもしくはフッ素ドープ酸化スズの皮膜を設けた光透過性の透明導電層から構成することができる。 The transparent electrode 1 is configured by forming a transparent conductive layer on a transparent substrate (not shown). As the transparent substrate, a general-purpose glass substrate, quartz substrate, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, and other transparent plastic substrates can be used. The transparent conductive layer is composed of tin oxide, fluorine-doped tin oxide, ITO, ATO, zinc oxide, aluminum-doped zinc oxide, or a light-transmissive transparent conductive layer in which a coating of tin oxide or fluorine-doped tin oxide is provided on the surface thereof. Can be configured.
電解質3としては、固体状、および液体状のものを用いることができる。具体的には、ヨウ素系電解質、臭素系電解質、セレン系電解質、硫黄系電解質、キノン/ヒドロキノン系電解質、およびコバルト錯体系電解質を用いることができる。これらに限定されないが、I2、LiI、ジメチルプロピルイミダゾリウムヨージド、t−ブチルピリジン、1,2−ジメチル−3−プロピルイミダゾリウムアイオダイド等を、アセトニトリル、メトキシアセトニトリル、プロピレンカーボネート、エチレンカーボネート、3−メトキシプロピオニル、炭酸プロピレン等の電気的に不活性な有機溶剤に溶かした溶液等が好適に用いられる。 As the electrolyte 3, a solid state or a liquid state can be used. Specifically, iodine-based electrolyte, bromine-based electrolyte, selenium-based electrolyte, sulfur-based electrolyte, quinone / hydroquinone-based electrolyte, and cobalt complex-based electrolyte can be used. But are not limited to, I 2, LiI, dimethylpropyl imidazolium iodide, t- butyl pyridine, 1,2-dimethyl-3-propyl imidazolium iodide, etc., acetonitrile, methoxy acetonitrile, propylene carbonate, ethylene carbonate, A solution or the like dissolved in an electrically inert organic solvent such as 3-methoxypropionyl or propylene carbonate is preferably used.
また、電解質組成物中の成分の揮発を低減する目的で、上述した電解質組成物にゲル化剤またはポリマー架橋モノマーを溶解させ、ゲル状電解質として使用してもよい。さらに上記電解質と可塑剤とを用いてポリマーに溶解させ、可塑剤を揮発除去することで全固体型の色素増感太陽電池を形成してもよい。 Further, for the purpose of reducing volatilization of components in the electrolyte composition, a gelling agent or a polymer crosslinking monomer may be dissolved in the electrolyte composition described above and used as a gel electrolyte. Further, an all-solid-state dye-sensitized solar cell may be formed by dissolving in the polymer using the electrolyte and the plasticizer and volatilizing and removing the plasticizer.
対電極4は、例えば、チタン、Al、SUS等の金属基板、ガラス基板またはプラスチック基板の上に形成される白金、カーボン、ニッケル、クロム、ステンレス、フッ素ドープ酸化スズおよびITOなどの導電層から構成される。また、対電極4は白金あるいはカーボンなどの触媒層(図示せず)を含んでもよく、さらに白金は硫黄材料で処理されていてもよい(例えば、特許文献9参照)。 The counter electrode 4 is composed of, for example, a conductive layer such as platinum, carbon, nickel, chromium, stainless steel, fluorine-doped tin oxide, and ITO formed on a metal substrate such as titanium, Al, and SUS, a glass substrate, or a plastic substrate. Is done. The counter electrode 4 may include a catalyst layer (not shown) such as platinum or carbon, and the platinum may be treated with a sulfur material (see, for example, Patent Document 9).
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。
1.フタロシアニン誘導体の合成
(フタロシアニン誘導体Aの合成)
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.
1. Synthesis of phthalocyanine derivative (Synthesis of phthalocyanine derivative A)
化合物1の合成Synthesis of compound 1
窒素雰囲気下、4,5−ジクロロフタロニトリル(19.0g、96.4mmol)、2,6−ジメチルフェノール(35.3g、289mmol)、炭酸カリウム(46.6g、337mmol)をDMF(190mL)に加え、100℃で16時間攪拌した。冷却後、水に分散し、析出した固体を濾取、減圧乾燥し粗生成物を得た。これをシリカゲルカラムクロマトグラフィーで精製した。ついで酢酸エチルを用いて再結晶を行い、化合物1(20.6g、55.4mmol、収率58%、白色固体)を得た。 Under a nitrogen atmosphere, 4,5-dichlorophthalonitrile (19.0 g, 96.4 mmol), 2,6-dimethylphenol (35.3 g, 289 mmol), potassium carbonate (46.6 g, 337 mmol) in DMF (190 mL). In addition, the mixture was stirred at 100 ° C. for 16 hours. After cooling, it was dispersed in water, and the precipitated solid was collected by filtration and dried under reduced pressure to obtain a crude product. This was purified by silica gel column chromatography. Subsequently, recrystallization was performed using ethyl acetate to obtain Compound 1 (20.6 g, 55.4 mmol, yield 58%, white solid).
化合物2の合成Synthesis of compound 2
窒素雰囲気下、4−ヨードフタロニトリル(11.1g、43.7mmol)、4−(メトキシカルボニル)フェニルボロン酸(15.7g、87.2mmol)、炭酸ナトリウム(18.5g、175mmol)、テトラキス(トリフェニルホスフィン)パラジウム(4.96g、4.3mmol)をDMF(480mL)と水(155mL)の混合溶液に加え、90℃で2時間攪拌した。冷却後、酢酸エチルおよび水を加え、有機相を抽出した。抽出した有機相を硫酸ナトリウムで乾燥後、減圧濃縮し粗生成物を得た。これをシリカゲルカラムクロマトグラフィーで精製し、化合物2(7.58g、28.9mmol、収率66%、白色固体)を得た。 Under a nitrogen atmosphere, 4-iodophthalonitrile (11.1 g, 43.7 mmol), 4- (methoxycarbonyl) phenylboronic acid (15.7 g, 87.2 mmol), sodium carbonate (18.5 g, 175 mmol), tetrakis ( Triphenylphosphine) palladium (4.96 g, 4.3 mmol) was added to a mixed solution of DMF (480 mL) and water (155 mL), and the mixture was stirred at 90 ° C. for 2 hours. After cooling, ethyl acetate and water were added and the organic phase was extracted. The extracted organic phase was dried over sodium sulfate and concentrated under reduced pressure to obtain a crude product. This was purified by silica gel column chromatography to obtain compound 2 (7.58 g, 28.9 mmol, 66% yield, white solid).
フタロシアニン誘導体Aの合成Synthesis of phthalocyanine derivative A
窒素雰囲気下、化合物1(34.15g、92.7mmol)、化合物2(8.11g、30.9mol)、塩化亜鉛(8.42g、61.8mmol)を2−ジメチルアミノエタノール1Lに加え、140℃で4時間攪拌した。冷却後、減圧濃縮し、残渣にメタノールを加えた。析出した固体を濾取、減圧乾燥し、粗生成物を得た。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製し、メチルエステル中間体を得た。 Under a nitrogen atmosphere, Compound 1 (34.15 g, 92.7 mmol), Compound 2 (8.11 g, 30.9 mol), and zinc chloride (8.42 g, 61.8 mmol) were added to 1 L of 2-dimethylaminoethanol. Stir at 4 ° C. for 4 hours. After cooling, the mixture was concentrated under reduced pressure, and methanol was added to the residue. The precipitated solid was collected by filtration and dried under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to obtain a methyl ester intermediate.
該中間体をTHF600mL、エタノール100mLおよび1mol/L水酸化ナトリウム水溶液100mLの混合溶液に溶解し、1時間加熱還流した。冷却後、塩酸で中和し、有機溶媒を減圧留去後、残渣をクロロホルムで抽出した。抽出した有機相を水洗し、硫酸ナトリウムで乾燥後、減圧濃縮し粗生成物を得た。これをシリカゲルカラムクロマトグラフィーで精製した。ついで酢酸エチルを用いて再結晶を行い、化合物A(4.66g、3.28mmol、収率11%、緑色固体、TOF−MS m/z1417[M+H]+)を得た。 The intermediate was dissolved in a mixed solution of 600 mL of THF, 100 mL of ethanol and 100 mL of 1 mol / L sodium hydroxide aqueous solution, and heated to reflux for 1 hour. After cooling, the mixture was neutralized with hydrochloric acid, the organic solvent was distilled off under reduced pressure, and the residue was extracted with chloroform. The extracted organic phase was washed with water, dried over sodium sulfate, and concentrated under reduced pressure to obtain a crude product. This was purified by silica gel column chromatography. Subsequently, recrystallization was performed using ethyl acetate to obtain Compound A (4.66 g, 3.28 mmol, yield 11%, green solid, TOF-MS m / z 1417 [M + H] + ).
(フタロシアニン誘導体Bの合成) (Synthesis of phthalocyanine derivative B)
窒素雰囲気下、化合物1(3.00g、8.14mmol)、塩化亜鉛(2.22g、16.3mmol)を2−ジメチルアミノエタノール60mLに加え、140℃で4時間撹拌した。冷却後、減圧濃縮し、残渣にメタノールを加え析出した固体を濾取した。得られた粗体をシリカゲルカラムクロマトグラフィーで精製し化合物B(1.06g、0.69mmol、収率34%、緑色固体、TOF−MS m/z1537[M+H]+)を得た。 Under a nitrogen atmosphere, Compound 1 (3.00 g, 8.14 mmol) and zinc chloride (2.22 g, 16.3 mmol) were added to 60 mL of 2-dimethylaminoethanol, and the mixture was stirred at 140 ° C. for 4 hours. After cooling, the mixture was concentrated under reduced pressure, methanol was added to the residue, and the precipitated solid was collected by filtration. The obtained crude product was purified by silica gel column chromatography to obtain Compound B (1.06 g, 0.69 mmol, yield 34%, green solid, TOF-MS m / z 1537 [M + H] + ).
(フタロシアニン誘導体Cの合成) (Synthesis of phthalocyanine derivative C)
化合物1(0.2g、0.54mmol)、塩化銅(0.036g、0.27mmol)を2−ジメチルアミノエタノール10mLに加え、140℃で2時間撹拌した。冷却後、減圧濃縮し、得られた粗体をシリカゲルカラムクロマトグラフィーで精製し化合物C(0.055g、0.035mmol、収率26%、緑色固体)を得た。 Compound 1 (0.2 g, 0.54 mmol) and copper chloride (0.036 g, 0.27 mmol) were added to 10 mL of 2-dimethylaminoethanol and stirred at 140 ° C. for 2 hours. After cooling, the mixture was concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography to obtain compound C (0.055 g, 0.035 mmol, yield 26%, green solid).
(フタロシアニン誘導体Dの合成)
化合物3の合成
(Synthesis of phthalocyanine derivative D)
Synthesis of compound 3
窒素雰囲気下、4,5−ジクロロフタロニトリル(2.0 g、10.2 mmol)、2,6−ジイソプロピルフェノール(4.6 g、25.8 mmol)、炭酸カリウム(3.8 g、27.5 mmol)をDMF(40mL)に加え、80〜100℃で12時間攪拌した。冷却後、水800 mLに分散し、析出した固体を濾取した。これを酢酸エチルに溶解させ、水洗した。有機層を硫酸ナトリウムで乾燥させた後、減圧濃縮し粗体を得た。これをメタノールでスラリー洗浄することにより化合物3(2.8g、5.8 mmol、収率57%、薄緑色固体)を得た。 Under a nitrogen atmosphere, 4,5-dichlorophthalonitrile (2.0 g, 10.2 mmol), 2,6-diisopropylphenol (4.6 g, 25.8 mmol), potassium carbonate (3.8 g, 27 0.5 mmol) was added to DMF (40 mL), and the mixture was stirred at 80 to 100 ° C. for 12 hours. After cooling, it was dispersed in 800 mL of water, and the precipitated solid was collected by filtration. This was dissolved in ethyl acetate and washed with water. The organic layer was dried over sodium sulfate and then concentrated under reduced pressure to obtain a crude product. This was slurry washed with methanol to obtain Compound 3 (2.8 g, 5.8 mmol, 57% yield, light green solid).
フタロシアニン誘導体Dの合成Synthesis of phthalocyanine derivative D
窒素雰囲気下、化合物3(2.00g、4.16mmol)、塩化亜鉛(1.13g、8.32mmol)を2−ジメチルアミノエタノール40mLに加え、140℃で4時間撹拌した。冷却後、減圧濃縮し、残渣にメタノールを加え析出した固体を濾取した。得られた粗体をシリカゲルカラムクロマトグラフィーで精製し化合物D(0.64g。0.32mmol、収率31%、緑色固体、TOF−MS m/z1986[M+H]+)を得た。 Under a nitrogen atmosphere, compound 3 (2.00 g, 4.16 mmol) and zinc chloride (1.13 g, 8.32 mmol) were added to 40 mL of 2-dimethylaminoethanol, and the mixture was stirred at 140 ° C. for 4 hours. After cooling, the mixture was concentrated under reduced pressure, methanol was added to the residue, and the precipitated solid was collected by filtration. The obtained crude product was purified by silica gel column chromatography to obtain compound D (0.64 g, 0.32 mmol, yield 31%, green solid, TOF-MS m / z 1986 [M + H] + ).
2.ポルフィリン誘導体の合成
(ポルフィリン誘導体P1の合成)
4‐(5‐ヘキシルチオフェン‐2‐イル)ベンズアルデヒドの合成
2. Synthesis of porphyrin derivative (synthesis of porphyrin derivative P1)
Synthesis of 4- (5-hexylthiophen-2-yl) benzaldehyde
反応容器に、4‐ブロモベンズアルデヒド(9.17g)、2‐(5‐ヘキシルチオフェン‐2‐イル)‐4,4,5,5‐テトラメチル‐1,3,2‐ジオキサボロラン(14.00g)、リン酸三カリウム(11.00g)、トルエン(150mL)と、ジクロロ[1,1‐ビス(ジフェニルホスフィノ)フェロセン]パラジウム(II)(0.20g)を加えて撹拌し、70℃に加熱した。反応終了後、反応液をセライトに通過させ、ろ液を濃縮した。これをシリカゲルカラム(クロロホルム)で展開分離し、生成物(4‐(5‐ヘキシルチオフェン‐2‐イル)ベンズアルデヒド、7.79g)を得た。 To the reaction vessel, 4-bromobenzaldehyde (9.17 g), 2- (5-hexylthiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (14.00 g) , Tripotassium phosphate (11.00 g), toluene (150 mL) and dichloro [1,1-bis (diphenylphosphino) ferrocene] palladium (II) (0.20 g) were added and stirred and heated to 70 ° C. did. After completion of the reaction, the reaction solution was passed through celite, and the filtrate was concentrated. This was developed and separated on a silica gel column (chloroform) to obtain a product (4- (5-hexylthiophen-2-yl) benzaldehyde, 7.79 g).
5‐(4‐メトキシカルボニルフェニル)‐10,15,20‐トリ[4‐(5‐ヘキシルチオフェン‐2‐イル)フェニル]ポルフィリンの合成Synthesis of 5- (4-methoxycarbonylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin
反応容器に、ピロール(0.92g)、4‐(5‐ヘキシルチオフェン‐2‐イル)ベンズアルデヒド(2.79g)、テレフタルアルデヒド酸メチル(0.56g)、クロロホルム(130mL)とエタノール(0.5ml)を加え、約10℃に冷却した。そこへ、三フッ化ホウ素(0.47g)を滴下し、そのまま2時間撹拌した。この溶液に、2,3‐ジクロロ‐5,6‐ジシアノ‐1,4‐ベンゾキノン(2.32g)を加え、さらに1時間撹拌した。反応液をセライトとシリカゲルに通過させ、ろ液を濃縮して粗成生物を得た。これをシリカゲルカラム(クロロホルム/ヘキサン=3/2)により展開分離し、生成物(5‐(4‐メトキシカルボニルフェニル)‐10,15,20‐トリ[4‐(5‐ヘキシルチオフェン‐2‐イル)フェニル]ポルフィリン、0.34g)を得た。 In a reaction vessel, pyrrole (0.92 g), 4- (5-hexylthiophen-2-yl) benzaldehyde (2.79 g), methyl terephthalaldehyde (0.56 g), chloroform (130 mL) and ethanol (0.5 ml) ) And cooled to about 10 ° C. Thereto, boron trifluoride (0.47 g) was added dropwise and stirred as such for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2.32 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform / hexane = 3/2), and the product (5- (4-methoxycarbonylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) was obtained. ) Phenyl] porphyrin, 0.34 g).
5‐(4‐メトキシカルボニルフェニル)‐10,15,20‐トリ[4‐(5‐ヘキシルチオフェン‐2‐イル)フェニル]ポルフィリン亜鉛(II)錯体の合成Synthesis of 5- (4-methoxycarbonylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin zinc (II) complex
5‐(4‐メトキシカルボニルフェニル)‐10,15,20‐トリ[4‐(5‐ヘキシルチオフェン‐2‐イル)フェニル]ポルフィリン(0.33g)をクロロホルム(16.5mL)に溶解させた。そこへ、メタノール(6mL)に溶解させた酢酸亜鉛二水和物(0.62g)を滴下した。反応終了をTLCで確認後、水を加えて分液した。有機相を水で洗浄し、無水硫酸ナトリウムで乾燥させた。溶媒を留去し、粗成生物を得た。これをシリカゲルカラム(クロロホルム)で展開分離し、紫色生成物(5‐(4‐メトキシカルボニルフェニル)‐10,15,20‐トリ[4‐(5‐ヘキシルチオフェン‐2‐イル)フェニル]ポルフィリン亜鉛(II)錯体、0.33g)を得た。 5- (4-Methoxycarbonylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin (0.33 g) was dissolved in chloroform (16.5 mL). Thereto, zinc acetate dihydrate (0.62 g) dissolved in methanol (6 mL) was added dropwise. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform), and the purple product (5- (4-methoxycarbonylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin zinc) (II) complex, 0.33 g) was obtained.
5‐(4‐カルボキシルフェニル)‐10,15,20‐トリ[4‐(5‐ヘキシルチオフェン‐2‐イル)フェニル]ポルフィリン亜鉛(II)錯体(ポルフィリン誘導体P1)の合成Synthesis of 5- (4-carboxylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin zinc (II) complex (porphyrin derivative P1)
5‐(4‐メトキシカルボニルフェニル)‐10,15,20‐トリ[4‐(5‐ヘキシルチオフェン‐2‐イル)フェニル]ポルフィリン亜鉛(II)錯体(0.31g)をTHF(30mL)と水(7mL)に溶解させた。そこへ48%水酸化ナトリウム(0.70g)を加え、原料が無くなるまで約68℃で加熱した。反応終了後、THFを留去した。残渣に3%ギ酸水を加え、弱酸性にした。紫色沈殿物を回収して、紫色生成物(5‐(4‐カルボキシルフェニル)‐10,15,20‐トリ[4‐(5‐ヘキシルチオフェン‐2‐イル)フェニル]ポルフィリン亜鉛(II)錯体、0.28g)を得た。
1H‐NMR(δH/ppm,THF,400MHz)0.96(t,9H),1.50‐1.40(m,18H),1.81(quin,6H),2.95(t,6H),6.92(d,3H),7.51(d,3H),8.00(d,6H),8.20(d,6H),8.31(d,2H),8.43(d,2H),8.84‐8.96(m,8H)
(ポルフィリン誘導体P2の合成)
2‐ホルミル‐5‐ヘキシルチオフェンの合成
5- (4-Methoxycarbonylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin zinc (II) complex (0.31 g) in THF (30 mL) and water (7 mL). Thereto was added 48% sodium hydroxide (0.70 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The purple precipitate was recovered and the purple product (5- (4-carboxylphenyl) -10,15,20-tri [4- (5-hexylthiophen-2-yl) phenyl] porphyrin zinc (II) complex, 0.28 g) was obtained.
1 H-NMR (δ H / ppm, THF, 400 MHz) 0.96 (t, 9H), 1.50-1.40 (m, 18H), 1.81 (quin, 6H), 2.95 (t , 6H), 6.92 (d, 3H), 7.51 (d, 3H), 8.00 (d, 6H), 8.20 (d, 6H), 8.31 (d, 2H), 8 .43 (d, 2H), 8.84-8.96 (m, 8H)
(Synthesis of porphyrin derivative P2)
Synthesis of 2-formyl-5-hexylthiophene
2‐ヘキシルチオフェン(20.0g)と脱水テトラヒドロフラン(100mL)を入れた反応容器を、−10℃まで冷却し、そこへn‐ブチルリチウム(90mL)を滴下した。2時間後、DMF(18mL)をゆっくり滴下した。この溶液を、10℃で1時間撹拌後、飽和塩化アンモニウム水溶液を滴下し、ヘキサンで抽出した。有機相を飽和塩化ナトリウム水溶液で洗浄し、無水硫酸ナトリウムで乾燥した。溶媒を留去して得られた油状物を、シリカゲルカラム(クロロホルム/ヘプタン=1/1)により展開分離し、生成物(2‐ホルミル‐5‐ヘキシルチオフェン、22.8g)を得た。 A reaction vessel containing 2-hexylthiophene (20.0 g) and dehydrated tetrahydrofuran (100 mL) was cooled to −10 ° C., and n-butyllithium (90 mL) was added dropwise thereto. After 2 hours, DMF (18 mL) was slowly added dropwise. After stirring this solution at 10 ° C. for 1 hour, a saturated aqueous ammonium chloride solution was added dropwise, and the mixture was extracted with hexane. The organic phase was washed with a saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. The oily substance obtained by distilling off the solvent was developed and separated by a silica gel column (chloroform / heptane = 1/1) to obtain the product (2-formyl-5-hexylthiophene, 22.8 g).
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリンの合成Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin
反応容器に、ピロール(2.73g)、2‐ホルミル‐5‐ヘキシルチオフェン(6.0g)、テレフタルアルデヒド酸メチル(1.67g)、クロロホルム(1500mL)とエタノール(6mL)を加え、約10℃に冷却した。そこへ、三フッ化ホウ素(1.45g)を滴下し、そのまま2時間撹拌した。この溶液に、2,3‐ジクロロ‐5,6‐ジシアノ‐1,4‐ベンゾキノン(6.94g)を加え、さらに1時間撹拌した。反応液をセライトとシリカゲルに通過させ、ろ液を濃縮して粗成生物を得た。これをシリカゲルカラム(クロロホルム/ヘキサン=3/1)により展開分離し、生成物(5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン、1.43g)を得た。 To a reaction vessel, pyrrole (2.73 g), 2-formyl-5-hexylthiophene (6.0 g), methyl terephthalaldehyde (1.67 g), chloroform (1500 mL) and ethanol (6 mL) were added, and about 10 ° C. Cooled to. Thereto was added boron trifluoride (1.45 g) dropwise, and the mixture was stirred for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (6.94 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform / hexane = 3/1), and the product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin, 1.43 g) was obtained.
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体の合成Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン(1.35g)をクロロホルム(160mL)に溶解させた。そこへ、メタノール(38mL)に溶解させた酢酸亜鉛二水和物(3.77g)を滴下した。反応終了をTLCで確認後、水を加えて分液した。有機相を水で洗浄し、無水硫酸ナトリウムで乾燥させた。溶媒を留去し、粗成生物を得た。これをシリカゲルカラム(クロロホルム)で展開分離し、紫色生成物(5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体、1.53g)を得た。 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin (1.35 g) was dissolved in chloroform (160 mL). Thereto was added dropwise zinc acetate dihydrate (3.77 g) dissolved in methanol (38 mL). After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex, 1.53 g) was obtained.
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐カルボキシルフェニル)ポルフィリン亜鉛(II)錯体(ポルフィリン誘導体P2)の合成Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-carboxylphenyl) porphyrin zinc (II) complex (porphyrin derivative P2)
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体(1.40g)をTHF(210mL)と水(70mL)に溶解させた。そこへ48%水酸化ナトリウム(7.0g)を加え、原料が無くなるまで約68℃で加熱した。反応終了後、THFを留去した。残渣に3%ギ酸水を加え、弱酸性にした。沈殿物を回収し、シリカゲルカラム(クロロホルム→クロロホルム/THF=5/1)で展開分離して、紫色生成物(5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐カルボキシルフェニル)ポルフィリン亜鉛(II)錯体、1.27g)を得た。
1H‐NMR(δH/ppm,CDCl3,400MHz)0.98(t,9H),1.45(m,12H),1.61(quin,6H),1.96(quin,6H),3.14(t,6H),7.17(d,3H),7.71(d,3H),8.35(d,2H),8.53(d,2H),8.89(d,2H),9.23(d,2H),9.24(s,4H)
5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex (1.40 g) dissolved in THF (210 mL) and water (70 mL) I let you. Thereto was added 48% sodium hydroxide (7.0 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The precipitate was collected, developed and separated on a silica gel column (chloroform → chloroform / THF = 5/1), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- ( 4-carboxylphenyl) porphyrin zinc (II) complex, 1.27 g) was obtained.
1 H-NMR (δ H / ppm, CDCl 3 , 400 MHz) 0.98 (t, 9H), 1.45 (m, 12H), 1.61 (quin, 6H), 1.96 (quin, 6H) , 3.14 (t, 6H), 7.17 (d, 3H), 7.71 (d, 3H), 8.35 (d, 2H), 8.53 (d, 2H), 8.89 ( d, 2H), 9.23 (d, 2H), 9.24 (s, 4H)
(ポルフィリン誘導体P3の合成)
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリンの合成
(Synthesis of porphyrin derivative P3)
Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin
反応容器に、ピロール(2.73g)、2‐ホルミル‐5‐ヘキシルチオフェン(6.0g)、テレフタルアルデヒド酸メチル(1.67g)、クロロホルム(1500mL)とエタノール(6mL)を加え、約10℃に冷却した。そこへ、三フッ化ホウ素(1.45g)を滴下し、そのまま2時間撹拌した。この溶液に、2,3‐ジクロロ‐5,6‐ジシアノ‐1,4‐ベンゾキノン(6.94g)を加え、さらに1時間撹拌した。反応液をセライトとシリカゲルに通過させ、ろ液を濃縮して粗成生物を得た。これをシリカゲルカラム(クロロホルム/ヘキサン=3/1)により展開分離し、生成物(5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン、1.43g)を得た。 To a reaction vessel, pyrrole (2.73 g), 2-formyl-5-hexylthiophene (6.0 g), methyl terephthalaldehyde (1.67 g), chloroform (1500 mL) and ethanol (6 mL) were added, and about 10 ° C. Cooled to. Thereto was added boron trifluoride (1.45 g) dropwise, and the mixture was stirred for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (6.94 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform / hexane = 3/1), and the product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin, 1.43 g) was obtained.
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン銅(II)錯体の合成Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin copper (II) complex
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン(0.53g)をクロロホルム(100mL)に溶解させた。そこへ、メタノール(40mL)に溶解させた酢酸銅(0.50g)を滴下した。反応終了をTLCで確認後、溶媒を留去し、粗成生物を得た。これをシリカゲルカラム(クロロホルム/ヘキサン=1/1)で展開分離し、紫色生成物(5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン銅(II)錯体、0.42g)を得た。 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin (0.53 g) was dissolved in chloroform (100 mL). Thereto, copper acetate (0.50 g) dissolved in methanol (40 mL) was added dropwise. After confirming the completion of the reaction by TLC, the solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform / hexane = 1/1), and a purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin was obtained. Copper (II) complex, 0.42 g) was obtained.
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐カルボキシルフェニル)ポルフィリン銅(II)錯体(ポルフィリン誘導体P3)の合成Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-carboxylphenyl) porphyrin copper (II) complex (porphyrin derivative P3)
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン銅(II)錯体(0.42g)をTHF(100mL)と水(10mL)に溶解させた。そこへ48%水酸化ナトリウム(1.50g)を加え、原料が無くなるまで約68℃で加熱した。反応終了後、THFを留去した。残渣に3%ギ酸水を加え、弱酸性にした。沈殿物を回収し、シリカゲルカラム(クロロホルム→クロロホルム/THF=5/1)で展開分離して、紫色生成物(5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐カルボキシルフェニル)ポルフィリン銅(II)錯体、0.40g)を得た。 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin copper (II) complex (0.42 g) dissolved in THF (100 mL) and water (10 mL) I let you. Thereto was added 48% sodium hydroxide (1.50 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The precipitate was collected, developed and separated on a silica gel column (chloroform → chloroform / THF = 5/1), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- ( 4-carboxylphenyl) porphyrin copper (II) complex, 0.40 g) was obtained.
(ポルフィリン誘導体P4の合成)
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリンコバルト(II)錯体の合成
(Synthesis of porphyrin derivative P4)
Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin cobalt (II) complex
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン(0.53g)をクロロホルム(100mL)に溶解させた。そこへ、メタノール(70mL)に溶解させた酢酸コバルト四水和物(0.70g)を滴下した。反応終了をTLCで確認後、溶媒を留去し、粗成生物を得た。これをシリカゲルカラム(クロロホルム/ヘキサン=1/2)で展開分離し、紫色生成物(5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリンコバルト(II)錯体、0.50g)を得た。 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin (0.53 g) was dissolved in chloroform (100 mL). Thereto was added dropwise cobalt acetate tetrahydrate (0.70 g) dissolved in methanol (70 mL). After confirming the completion of the reaction by TLC, the solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform / hexane = 1/2), and a purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin was obtained. Cobalt (II) complex, 0.50 g) was obtained.
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐カルボキシルフェニル)ポルフィリンコバルト(II)錯体(ポルフィリン誘導体P4)の合成Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-carboxylphenyl) porphyrin cobalt (II) complex (porphyrin derivative P4)
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリンコバルト(II)錯体(0.50g)をTHF(150mL)と水(15mL)に溶解させた。そこへ48%水酸化ナトリウム(2.00g)を加え、原料が無くなるまで約68℃で加熱した。反応終了後、THFを留去した。残渣に3%ギ酸水を加え、弱酸性にした。沈殿物を回収し、シリカゲルカラム(クロロホルム→クロロホルム/THF=5/1)で展開分離して、紫色生成物(5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐カルボキシルフェニル)ポルフィリンコバルト(II)錯体、0.29g)を得た。 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin cobalt (II) complex (0.50 g) dissolved in THF (150 mL) and water (15 mL) I let you. Thereto was added 48% sodium hydroxide (2.00 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The precipitate was collected, developed and separated on a silica gel column (chloroform → chloroform / THF = 5/1), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- ( 4-carboxylphenyl) porphyrin cobalt (II) complex, 0.29 g).
(ポルフィリン誘導体P5の合成)
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐カルボキシルフェニル)ポルフィリン(ポルフィリン誘導体P5)の合成
(Synthesis of porphyrin derivative P5)
Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-carboxylphenyl) porphyrin (porphyrin derivative P5)
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン(0.15g)をTHF(50mL)と水(10mL)に溶解させた。そこへ48%水酸化ナトリウム(1.50g)を加え、原料が無くなるまで約68℃で加熱した。反応終了後、THFを留去した。残渣に3%ギ酸水を加え、弱酸性にした。沈殿物を回収し、シリカゲルカラム(クロロホルム→クロロホルム/THF=5/1)で展開分離して、紫色生成物(5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐カルボキシルフェニル)ポルフィリン、0.10g)を得た。
1H‐NMR(δH/ppm,CDCl3,400MHz)0.98(t,9H),1.40‐1.50(m,12H),1.60(quin,6H),1.96(quin,6H),3.14(t,6H),7.17(d,3H),7.71(d,3H),8.35(d,2H),8.54(d,2H),8.78‐9.14(m,8H)
5,10,15-tri (5-hexylthiophen-2-yl) -20- (4-methoxycarbonylphenyl) porphyrin (0.15 g) was dissolved in THF (50 mL) and water (10 mL). Thereto was added 48% sodium hydroxide (1.50 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The precipitate was collected, developed and separated on a silica gel column (chloroform → chloroform / THF = 5/1), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- ( 4-carboxylphenyl) porphyrin, 0.10 g).
1 H-NMR (δ H / ppm, CDCl 3 , 400 MHz) 0.98 (t, 9H), 1.40-1.50 (m, 12H), 1.60 (quin, 6H), 1.96 ( quin, 6H), 3.14 (t, 6H), 7.17 (d, 3H), 7.71 (d, 3H), 8.35 (d, 2H), 8.54 (d, 2H), 8.78-9.14 (m, 8H)
(ポルフィリン誘導体P6の合成)
5‐ホルミルチオフェン‐2‐カルボン酸メチルエステルの合成
(Synthesis of porphyrin derivative P6)
Synthesis of 5-formylthiophene-2-carboxylic acid methyl ester
反応容器に、5‐ホルミルチオフェン‐2‐カルボン酸(0.50g)、4‐ジメチルアミノピリジン(0.11g)、メタノール(0.87g)とクロロホルム(12mL)を加え、5℃まで冷却した。そこへ1‐(3‐ジメチルアミノプロピル)‐3‐エチルカルボジイミド塩酸塩(0.74g)を加えた。室温で1時間撹拌後、3mol/L塩酸(8mL)を投入した。反応液をクロロホルムで抽出し、有機層を飽和食塩水で洗浄した。有機相を無水硫酸ナトリウムで乾燥し、溶媒を留去して粗生成物を得た。これをシリカゲルカラム(クロロホルム)で精製し、黄色生成物(5‐ホルミルチオフェン‐2‐カルボン酸メチルエステル、0.45g)を得た。 To the reaction vessel, 5-formylthiophene-2-carboxylic acid (0.50 g), 4-dimethylaminopyridine (0.11 g), methanol (0.87 g) and chloroform (12 mL) were added and cooled to 5 ° C. 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (0.74 g) was added thereto. After stirring at room temperature for 1 hour, 3 mol / L hydrochloric acid (8 mL) was added. The reaction solution was extracted with chloroform, and the organic layer was washed with saturated brine. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain a crude product. This was purified by a silica gel column (chloroform) to obtain a yellow product (5-formylthiophene-2-carboxylic acid methyl ester, 0.45 g).
5‐(5‐メトキシカルボニルチオフェン‐2‐イル)‐10,15,20‐トリ(5‐ヘキシルチオフェン‐2‐イル)ポルフィリンの合成Synthesis of 5- (5-methoxycarbonylthiophen-2-yl) -10,15,20-tri (5-hexylthiophen-2-yl) porphyrin
反応容器に、ピロール(1.26g)、2‐ホルミル‐5‐ヘキシルチオフェン(2.77g)、5‐ホルミルチオフェン‐2‐カルボン酸メチルエステル(0.80g)、クロロホルム(700mL)とエタノール(3mL)を加え、約10℃に冷却した。そこへ、三フッ化ホウ素(0.67g)を滴下し、そのまま2時間撹拌した。この溶液に、2,3‐ジクロロ‐5,6‐ジシアノ‐1,4‐ベンゾキノン(3.20g)を加え、さらに1時間撹拌した。反応液をセライトとシリカゲルに通し、ろ液を濃縮して粗成生物を得た。これをシリカゲルカラム(クロロホルム/ヘキサン=3/2→5/1)により展開分離し、生成物(5‐(5‐メトキシカルボニルチオフェン‐2‐イル)‐10,15,20‐トリ(5‐ヘキシルチオフェン‐2‐イル)ポルフィリン、1.43g)を得た。 In a reaction vessel, pyrrole (1.26 g), 2-formyl-5-hexylthiophene (2.77 g), 5-formylthiophene-2-carboxylic acid methyl ester (0.80 g), chloroform (700 mL) and ethanol (3 mL ) And cooled to about 10 ° C. Thereto, boron trifluoride (0.67 g) was added dropwise and stirred as such for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (3.20 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform / hexane = 3/2 → 5/1), and the product (5- (5-methoxycarbonylthiophen-2-yl) -10,15,20-tri (5-hexyl) was separated. Thiophen-2-yl) porphyrin, 1.43 g) was obtained.
5‐(5‐メトキシカルボニルチオフェン‐2‐イル)‐10,15,20‐トリ(5‐ヘキシルチオフェン‐2‐イル)ポルフィリン亜鉛(II)錯体の合成Synthesis of 5- (5-methoxycarbonylthiophen-2-yl) -10,15,20-tri (5-hexylthiophen-2-yl) porphyrin zinc (II) complex
5‐(5‐メトキシカルボニルチオフェン‐2‐イル)‐10,15,20‐トリ(5‐ヘキシルチオフェン‐2‐イル)ポルフィリン(0.50g)をクロロホルム(60mL)に溶解させた。そこへ、メタノール(14mL)に溶解させた酢酸亜鉛二水和物(1.39g)を滴下した。反応終了をTLCで確認後、水を加えて分液した。有機相を水で洗浄し、無水硫酸ナトリウムで乾燥させた。溶媒を留去し、粗成生物を得た。これをシリカゲルカラム(クロロホルム)で展開分離し、紫色生成物(5‐(5‐メトキシカルボニルチオフェン‐2‐イル)‐10,15,20‐トリ(5‐ヘキシルチオフェン‐2‐イル)ポルフィリン亜鉛(II)錯体、0.42g)を得た。 5- (5-Methoxycarbonylthiophen-2-yl) -10,15,20-tri (5-hexylthiophen-2-yl) porphyrin (0.50 g) was dissolved in chloroform (60 mL). There, the zinc acetate dihydrate (1.39g) dissolved in methanol (14mL) was dripped. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform), and the purple product (5- (5-methoxycarbonylthiophen-2-yl) -10,15,20-tri (5-hexylthiophen-2-yl) porphyrin zinc ( II) Complex, 0.42 g) was obtained.
5‐(5‐カルボキシルチオフェン‐2‐イル)‐10,15,20‐トリ(5‐ヘキシルチオフェン‐2‐イル)ポルフィリン亜鉛(II)錯体(ポルフィリン誘導体P6)の合成Synthesis of 5- (5-carboxylthiophen-2-yl) -10,15,20-tri (5-hexylthiophen-2-yl) porphyrin zinc (II) complex (porphyrin derivative P6)
5‐(5‐メトキシカルボニルチオフェン‐2‐イル)‐10,15,20‐トリ(5‐ヘキシルチオフェン‐2‐イル)ポルフィリン亜鉛(II)錯体(0.41g)をTHF(60mL)と水(20mL)に溶解させた。そこへ48%水酸化ナトリウム(2.00g)を加え、原料が無くなるまで約68℃で加熱した。反応終了後、THFを留去した。残渣に3%ギ酸水を加え、弱酸性にした。クロロホルムで抽出し、無水硫酸ナトリウムで乾燥させた。溶媒を留去し、シリカゲルカラム(クロロホルム→クロロホルム/THF=5/1)で展開分離して、紫色生成物(5‐(5‐カルボキシルチオフェン‐2‐イル)‐10,15,20‐トリ(5‐ヘキシルチオフェン‐2‐イル)ポルフィリン亜鉛(II)錯体、0.40g)を得た。
1H‐NMR(δH/ppm,CDCl3,400MHz)0.98(t,9H),1.41‐1.47(m,12H),1.60(quin,6H),1.96(quin,6H),3.14(t,6H),7.17(d,3H),7.70(d,3H),7.94(d,2H),8.26(d,2H),9.12(d,2H),9.23(s,4H),9.26(d,2H)
5- (5-Methoxycarbonylthiophen-2-yl) -10,15,20-tri (5-hexylthiophen-2-yl) porphyrin zinc (II) complex (0.41 g) in THF (60 mL) and water ( 20 mL). Thereto was added 48% sodium hydroxide (2.00 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. Extracted with chloroform and dried over anhydrous sodium sulfate. The solvent was distilled off and the residue was developed and separated on a silica gel column (chloroform → chloroform / THF = 5/1) to give a purple product (5- (5-carboxylthiophen-2-yl) -10,15,20-tri ( 5-hexylthiophen-2-yl) porphyrin zinc (II) complex, 0.40 g) was obtained.
1 H-NMR (δ H / ppm, CDCl 3 , 400 MHz) 0.98 (t, 9H), 1.41-1.47 (m, 12H), 1.60 (quin, 6H), 1.96 ( quin, 6H), 3.14 (t, 6H), 7.17 (d, 3H), 7.70 (d, 3H), 7.94 (d, 2H), 8.26 (d, 2H), 9.12 (d, 2H), 9.23 (s, 4H), 9.26 (d, 2H)
(ポルフィリン誘導体P7の合成)
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐(4'‐メトキシカルボニル)ビフェニル)ポルフィリンの合成
(Synthesis of porphyrin derivative P7)
Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4'-methoxycarbonyl) biphenyl) porphyrin
反応容器に、ピロール(1.07g)、2‐ホルミル‐5‐ヘキシルチオフェン(2.35g)、4'‐ホルミルビフェニル‐4‐カルボン酸メチルエステル(0.96g)、クロロホルム(120mL)とエタノール(3mL)を加え、約10℃に冷却した。そこへ、三フッ化ホウ素(0.57g)を滴下し、そのまま2時間撹拌した。この溶液に、2,3‐ジクロロ‐5,6‐ジシアノ‐1,4‐ベンゾキノン(2.80g)を加え、さらに1時間撹拌した。反応液をセライトとシリカゲルに通過させ、ろ液を濃縮して粗成生物を得た。これをシリカゲルカラム(クロロホルム)により展開分離し、生成物(5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐(4'‐メトキシカルボニル)ビフェニル)ポルフィリン、0.40g)を得た。 In a reaction vessel, pyrrole (1.07 g), 2-formyl-5-hexylthiophene (2.35 g), 4′-formylbiphenyl-4-carboxylic acid methyl ester (0.96 g), chloroform (120 mL) and ethanol ( 3 mL) was added and cooled to about 10 ° C. To this, boron trifluoride (0.57 g) was added dropwise and stirred as such for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2.80 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform), and the product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4′-methoxycarbonyl) biphenyl) porphyrin, 0 .40 g) was obtained.
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐(4'‐メトキシカルボニル)ビフェニル)ポルフィリン亜鉛(II)錯体の合成Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4'-methoxycarbonyl) biphenyl) porphyrin zinc (II) complex
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐(4'‐メトキシカルボニル)ビフェニル)ポルフィリン(0.40g)をクロロホルム(100mL)に溶解させた。そこへ、メタノール(40ml)に溶解させた酢酸亜鉛二水和物(0.60g)を滴下した。反応終了をTLCで確認後、水を加えて分液した。有機相を水で洗浄し、無水硫酸ナトリウムで乾燥させた。溶媒を留去し、粗成生物を得た。これをシリカゲルカラム(クロロホルム)で展開分離し、紫色生成物(5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐(4'‐メトキシカルボニル)ビフェニル)ポルフィリン亜鉛(II)錯体、0.40g)を得た。 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4′-methoxycarbonyl) biphenyl) porphyrin (0.40 g) was dissolved in chloroform (100 mL). Thereto was added dropwise zinc acetate dihydrate (0.60 g) dissolved in methanol (40 ml). After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4′-methoxycarbonyl) biphenyl) porphyrin zinc (II) complex, 0.40 g) was obtained.
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐(4'‐カルボキシル)ビフェニル)ポルフィリン亜鉛(II)錯体(ポルフィリン誘導体P7)の合成Synthesis of 5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4′-carboxyl) biphenyl) porphyrin zinc (II) complex (porphyrin derivative P7)
5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐(4'‐メトキシカルボニル)ビフェニル)ポルフィリン亜鉛(II)錯体(0.40g)をTHF(70mL)と水(30mL)に溶解させた。そこへ48%水酸化ナトリウム(3.00g)を加え、原料が無くなるまで約68℃で加熱した。反応終了後、THFを留去した。残渣に3%ギ酸水を加え、弱酸性にした。沈殿物を回収し、シリカゲルカラム(クロロホルム→クロロホルム/酢酸エチル=5/1)で展開分離して、紫色生成物(5,10,15‐トリ(5‐ヘキシルチオフェン‐2‐イル)‐20‐(4‐(4'‐カルボキシル)ビフェニル)ポルフィリン亜鉛(II)錯体、0.37g)を得た。
1H‐NMR(δH/ppm,CDCl3,400MHz)0.96‐1.00(m,9H),1.44‐1.46(m,12H),1.60(quin,6H),1.96(quin,6H),3.14(t,6H),7.17(d,3H),7.70(d,3H),8.04(d,4H),8.33(d,4H),8.98‐9.25(m,8H)
5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4′-methoxycarbonyl) biphenyl) porphyrin zinc (II) complex (0.40 g) in THF (70 mL) and water (30 mL). Thereto was added 48% sodium hydroxide (3.00 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The precipitate was collected, developed and separated on a silica gel column (chloroform → chloroform / ethyl acetate = 5/1), and the purple product (5,10,15-tri (5-hexylthiophen-2-yl) -20- (4- (4′-carboxyl) biphenyl) porphyrin zinc (II) complex, 0.37 g) was obtained.
1 H-NMR (δ H / ppm, CDCl 3 , 400 MHz) 0.96-1.00 (m, 9H), 1.44-1.46 (m, 12H), 1.60 (quin, 6H), 1.96 (quin, 6H), 3.14 (t, 6H), 7.17 (d, 3H), 7.70 (d, 3H), 8.04 (d, 4H), 8.33 (d , 4H), 8.98-9.25 (m, 8H)
(ポルフィリン誘導体P8の合成)
2‐(4‐ヘキシルフェニル)‐4,4,5,5‐テトラメチル‐1,3,2‐ジオキサボロランの合成
(Synthesis of porphyrin derivative P8)
Synthesis of 2- (4-hexylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane
反応容器に、1‐ブロモ‐4‐ヘキシルベンゼン(10.00g)、ビス(ピナコレート)ジボラン(12.60g)、酢酸カリウム(12.13g)とDMF(200mL)を加えて撹拌した。そこへビス(トリフェニルホスフィン)パラジウム(II)ジクロリド(0.61g)を投入して80℃に加温した。一晩加熱撹拌した後、クロロホルムと水を加えて分液洗浄した。有機相を無水硫酸ナトリウムで乾燥させ、溶媒を留去した。これをシリカゲルカラム(ヘキサン→ヘキサン/クロロホルム=1/2)で精製して、生成物(2‐(4‐ヘキシルフェニル)‐4,4,5,5‐テトラメチル‐1,3,2‐ジオキサボロラン、9.30g)を得た。 To the reaction vessel, 1-bromo-4-hexylbenzene (10.00 g), bis (pinacolato) diborane (12.60 g), potassium acetate (12.13 g) and DMF (200 mL) were added and stirred. Bis (triphenylphosphine) palladium (II) dichloride (0.61 g) was added thereto and heated to 80 ° C. After heating and stirring overnight, chloroform and water were added to separate and wash. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off. This was purified with a silica gel column (hexane → hexane / chloroform = 1/2) to give the product (2- (4-hexylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane. 9.30 g).
5‐(4‐ヘキシルフェニル)チオフェン‐2‐カルバルデヒドの合成Synthesis of 5- (4-hexylphenyl) thiophene-2-carbaldehyde
反応容器に2‐(4‐ヘキシルフェニル)‐4,4,5,5‐テトラメチル‐1,3,2‐ジオキサボロラン(5.10g)、5‐ブロモチオフェン‐2‐カルバルデヒド(4.07g)、10%炭酸ナトリウム水溶液(55mL)とジオキサン(60mL)を加えて撹拌した。そこへテトラキストリフェニルホスフィンパラジウム(598mg)を投入し、80℃に加温した。一晩加熱撹拌した後、クロロホルムと水を加えて分液洗浄した。有機相を無水硫酸ナトリウムで乾燥させ、溶媒を留去した。これをシリカゲルカラム(ヘキサン/クロロホルム=4/1→クロロホルム)で精製して、生成物(5‐(4‐ヘキシルフェニル)チオフェン‐2‐カルバルデヒド、4.70g)を得た。 2- (4-Hexylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.10 g), 5-bromothiophene-2-carbaldehyde (4.07 g) in a reaction vessel A 10% aqueous sodium carbonate solution (55 mL) and dioxane (60 mL) were added and stirred. Tetrakistriphenylphosphine palladium (598 mg) was added thereto and heated to 80 ° C. After heating and stirring overnight, chloroform and water were added to separate and wash. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off. This was purified by a silica gel column (hexane / chloroform = 4/1 → chloroform) to obtain a product (5- (4-hexylphenyl) thiophene-2-carbaldehyde, 4.70 g).
5,10,15‐トリ[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリンの合成Synthesis of 5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin
ピロール(1.58g)、5‐(4‐ヘキシルフェニル)チオフェン‐2‐カルバルデヒド(4.80g)、テレフタルアルデヒド酸メチル(0.97g)をクロロホルム(180mL)とエタノール(3mL)に溶解させ、約10℃に冷却した。そこへ、三フッ化ホウ素(0.83g)を滴下し、そのまま2時間撹拌した。この溶液に、2,3‐ジクロロ‐5,6‐ジシアノ‐1,4‐ベンゾキノン(4.10g)を入れ、さらに1時間撹拌した。反応液をセライトとシリカゲルに通過させ、ろ液を濃縮して粗成生物を得た。これをシリカゲルカラム(クロロホルム)により展開分離し、生成物(5,10,15‐トリ[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン、0.50g)を得た。 Pyrrole (1.58 g), 5- (4-hexylphenyl) thiophene-2-carbaldehyde (4.80 g), methyl terephthalaldehyde (0.97 g) were dissolved in chloroform (180 mL) and ethanol (3 mL), Cooled to about 10 ° C. Thereto was added boron trifluoride (0.83 g) dropwise, and the mixture was stirred as it was for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (4.10 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform), and the product (5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin, 0 .50 g) was obtained.
5,10,15‐トリ[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体の合成Synthesis of 5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex
5,10,15‐トリ[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン(0.50g)をクロロホルム(120mL)に溶解させた。そこへ、メタノール(60mL)に溶解させた酢酸亜鉛二水和物(0.70g)を滴下した。反応終了をTLCで確認後、水を加えて分液した。有機相を水で洗浄し、無水硫酸ナトリウムで乾燥させた。溶媒を留去し、粗成生物を得た。これをシリカゲルカラム(ヘキサン/クロロホルム=2/1)で展開分離し、紫色生成物(5,10,15‐トリ[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体、0.40g)を得た。 5,10,15-Tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin (0.50 g) was dissolved in chloroform (120 mL). There, the zinc acetate dihydrate (0.70g) dissolved in methanol (60 mL) was dripped. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (hexane / chloroform = 2/1), and the purple product (5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4- Methoxycarbonylphenyl) porphyrin zinc (II) complex, 0.40 g) was obtained.
5,10,15‐トリ[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]‐20‐(4‐カルボキシルフェニル)ポルフィリン亜鉛(II)錯体の(ポルフィリン誘導体P8)合成Synthesis of (porphyrin derivative P8) of 5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-carboxylphenyl) porphyrin zinc (II) complex
5,10,15‐トリ[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体(0.40g)をTHF(50mL)と水(30mL)に溶解させた。そこへ48%水酸化ナトリウム(3mL)を加え、約68℃で加熱した。反応終了後、THFを留去した。残渣に3%ギ酸水を加え、弱酸性にした。クロロホルムで抽出し、有機相を水洗した。有機層を無水硫酸ナトリウムで乾燥させて溶媒を留去した。これをシリカゲルカラム(クロロホルム→クロロホルム/酢酸エチル=4/1)で精製して、紫色生成物(5,10,15‐トリ[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]‐20‐(4‐カルボキシルフェニル)ポルフィリン亜鉛(II)錯体、0.30g)を得た。
1H‐NMR(δH/ppm,CDCl3,400MHz)0.92(t,9H),1.30‐1.42(m,18H),1.69(quin,6H),2.69(t,6H),7.31(d,6H),7.67(d,3H),7.79(d,6H),7.87(d,3H),8.36(d,2H),8.52(d,2H),8.91‐9.34(m,8H)
5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex (0.40 g) in THF (50 mL) and water (30 mL). 48% sodium hydroxide (3 mL) was added thereto, and the mixture was heated at about 68 ° C. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. Extraction was performed with chloroform, and the organic phase was washed with water. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off. This was purified with a silica gel column (chloroform → chloroform / ethyl acetate = 4/1) to give a purple product (5,10,15-tri [5- (4-hexylphenyl) thiophen-2-yl] -20- (4-carboxylphenyl) porphyrin zinc (II) complex, 0.30 g) was obtained.
1 H-NMR (δ H / ppm, CDCl 3 , 400 MHz) 0.92 (t, 9H), 1.30-1.42 (m, 18H), 1.69 (quin, 6H), 2.69 ( t, 6H), 7.31 (d, 6H), 7.67 (d, 3H), 7.79 (d, 6H), 7.87 (d, 3H), 8.36 (d, 2H), 8.52 (d, 2H), 8.91-9.34 (m, 8H)
(ポルフィリン誘導体P9の合成)
9‐(2‐チオフェン)‐3,6‐ジ‐t‐ブチルカルバゾールの合成
(Synthesis of porphyrin derivative P9)
Synthesis of 9- (2-thiophene) -3,6-di-t-butylcarbazole
反応容器に、3,6‐ジ‐t‐ブチルカルバゾール(12.46g)、銅(8.23g)、炭酸カリウム(8.15g)、2‐ブロモチオフェン(8.73g)とニトロベンゼン(100mL)を加え、160℃で1日加熱撹拌した。反応液にクロロホルムを投入し、セライト中を通過させた。ろ液を濃縮し、シリカゲルカラム(クロロホルム/ヘキサン=1/2)で分離精製して、生成物(9‐(2‐チオフェン)‐3,6‐ジ‐t‐ブチルカルバゾール、6.75g)を得た。 In a reaction vessel, 3,6-di-t-butylcarbazole (12.46 g), copper (8.23 g), potassium carbonate (8.15 g), 2-bromothiophene (8.73 g) and nitrobenzene (100 mL) were added. In addition, the mixture was stirred at 160 ° C. for 1 day. Chloroform was added to the reaction solution and allowed to pass through Celite. The filtrate was concentrated and separated and purified on a silica gel column (chloroform / hexane = 1/2) to give the product (9- (2-thiophene) -3,6-di-t-butylcarbazole, 6.75 g). Obtained.
9‐[(2‐ホルミル)チオフェン‐5‐イル]‐3,6‐ジ‐t‐ブチルカルバゾールの合成Synthesis of 9-[(2-formyl) thiophen-5-yl] -3,6-di-tert-butylcarbazole
9‐(2‐チオフェン)‐3,6‐ジ‐t‐ブチルカルバゾール(6.75g)を脱水THF(50mL)に溶解させ、0℃まで冷却した。そこへn‐ブチルリチウム(13mL)をゆっくりと滴下した。30分後、DMF(1.6mL)を投入した。反応液に飽和塩化アンモニウム水溶液を加え、酢酸エチルで抽出した。有機相を飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥させた。溶媒を留去し、シリカゲルカラム(ヘキサン/酢酸エチル=20/1→10/1→8/1)で精製して、黄色生成物(9‐[(2‐ホルミル)チオフェン‐5‐イル]‐3,6‐ジ‐t‐ブチルカルバゾール、5.65g)を得た。 9- (2-thiophene) -3,6-di-t-butylcarbazole (6.75 g) was dissolved in dehydrated THF (50 mL) and cooled to 0 ° C. N-Butyllithium (13 mL) was slowly added dropwise thereto. After 30 minutes, DMF (1.6 mL) was added. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic phase was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column (hexane / ethyl acetate = 20/1 → 10/1 → 8/1) to give a yellow product (9-[(2-formyl) thiophen-5-yl]- 3,6-di-t-butylcarbazole (5.65 g) was obtained.
5,10,15‐トリ[5‐(3,6‐ジ‐t‐ブチル‐9H‐カルバゾール‐9‐イル)チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリンの合成Synthesis of 5,10,15-tri [5- (3,6-di-tert-butyl-9H-carbazol-9-yl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin
反応容器に、ピロール(0.62g)、テレフタルアルデヒド酸メチル(0.38g)、9‐[(2‐ホルミル)チオフェン‐5‐イル]‐3,6‐ジ‐t‐ブチルカルバゾール(2.70g)、クロロホルム(150mL)とエタノール(2mL)を入れ、約10℃に冷却した。そこへ、三フッ化ホウ素(0.36g)を滴下し、そのまま2時間撹拌した。この溶液に、2,3‐ジクロロ‐5,6‐ジシアノ‐1,4‐ベンゾキノン(1.70g)を加え、さらに1時間撹拌した。反応液をセライトとシリカゲルに通過させ、ろ液を濃縮して粗成生物を得た。これをシリカゲルカラム(クロロホルム)により展開分離し、生成物(5,10,15‐トリ[5‐(3,6‐ジ‐t‐ブチル‐9H‐カルバゾール‐9‐イル)チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン、0.98g)を得た。 In a reaction vessel, pyrrole (0.62 g), methyl terephthalaldehyde (0.38 g), 9-[(2-formyl) thiophen-5-yl] -3,6-di-t-butylcarbazole (2.70 g) ), Chloroform (150 mL) and ethanol (2 mL) were added and cooled to about 10 ° C. To this, boron trifluoride (0.36 g) was added dropwise and stirred as such for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (1.70 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform), and the product (5,10,15-tri [5- (3,6-di-t-butyl-9H-carbazol-9-yl) thiophen-2-yl] was obtained. -20- (4-methoxycarbonylphenyl) porphyrin, 0.98 g).
5,10,15‐トリ[5‐(3,6‐ジ‐t‐ブチル‐9H‐カルバゾール‐9‐イル)チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体の合成5,10,15-tri [5- (3,6-di-tert-butyl-9H-carbazol-9-yl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) Complex synthesis
5,10,15‐トリ[5‐(3,6‐ジ‐t‐ブチル‐9H‐カルバゾール‐9‐イル)チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン(0.98g)をクロロホルム(100mL)に溶解させた。そこへ、メタノール(40mL)に溶解させた酢酸亜鉛二水和物(0.70g)を滴下した。反応終了をTLCで確認後、水を加えて分液した。有機相を水で洗浄し、無水硫酸ナトリウムで乾燥させた。溶媒を留去し、粗成生物を得た。これをシリカゲルカラム(クロロホルム)で展開分離し、紫色生成物(5,10,15‐トリ[5‐(3,6‐ジ‐t‐ブチル‐9H‐カルバゾール‐9‐イル)チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体、1.00g)を得た。 5,10,15-tri [5- (3,6-di-t-butyl-9H-carbazol-9-yl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin (0.98 g ) Was dissolved in chloroform (100 mL). Thereto, zinc acetate dihydrate (0.70 g) dissolved in methanol (40 mL) was added dropwise. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (chloroform), and the purple product (5,10,15-tri [5- (3,6-di-t-butyl-9H-carbazol-9-yl) thiophen-2-yl] was isolated. ] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex, 1.00 g) was obtained.
5,10,15‐トリ[5‐(3,6‐ジ‐t‐ブチル‐9H‐カルバゾール‐9‐イル)チオフェン‐2‐イル]‐20‐(4‐カルボキシルフェニル)ポルフィリン亜鉛(II)錯体(ポルフィリン誘導体P9)の合成5,10,15-tri [5- (3,6-di-t-butyl-9H-carbazol-9-yl) thiophen-2-yl] -20- (4-carboxylphenyl) porphyrin zinc (II) complex Synthesis of (porphyrin derivative P9)
5,10,15‐トリ[5‐(3,6‐ジ‐t‐ブチル‐9H‐カルバゾール‐9‐イル)チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体(1.00g)をTHF(150mL)と水(15mL)に溶解させた。そこへ48%水酸化ナトリウム(1.5g)を加え、原料が無くなるまで約68℃で加熱した。反応終了後、THFを留去した。残渣に3%ギ酸水を加え、弱酸性にした。紫色沈殿物を回収して、紫色生成物(5,10,15‐トリ[5‐(3,6‐ジ‐t‐ブチル‐9H‐カルバゾール‐9‐イル)チオフェン‐2‐イル]‐20‐(4‐カルボキシルフェニル)ポルフィリン亜鉛(II)錯体、0.70g)を得た。
1H‐NMR(δH/ppm,CDCl3,400MHz)1.53(s,54H),7.63(dd,3H),7.67(t,6H),7.88(t,6H),8.01(dd,3H),8.22(s,6H),8.41(d,2H),8.59(d,2H),9.02(d,2H),9.42(d,2H),9.48(s,4H)
5,10,15-tri [5- (3,6-di-tert-butyl-9H-carbazol-9-yl) thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) The complex (1.00 g) was dissolved in THF (150 mL) and water (15 mL). Thereto was added 48% sodium hydroxide (1.5 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The purple precipitate was recovered and the purple product (5,10,15-tri [5- (3,6-di-tert-butyl-9H-carbazol-9-yl) thiophen-2-yl] -20- (4-Carboxyphenyl) porphyrin zinc (II) complex, 0.70 g) was obtained.
1 H-NMR (δ H / ppm, CDCl 3 , 400 MHz) 1.53 (s, 54H), 7.63 (dd, 3H), 7.67 (t, 6H), 7.88 (t, 6H) , 8.01 (dd, 3H), 8.22 (s, 6H), 8.41 (d, 2H), 8.59 (d, 2H), 9.02 (d, 2H), 9.42 ( d, 2H), 9.48 (s, 4H)
(ポルフィリン誘導体P10の合成)
5‐ブロモ‐5'‐ホルミル‐2,2'‐ビチオフェンの合成
(Synthesis of porphyrin derivative P10)
Synthesis of 5-bromo-5'-formyl-2,2'-bithiophene
5‐ホルミル‐2,2'‐ビチオフェン(5.00g)をDMF(6mL)に溶解させ、0℃に冷却した。そこへN‐ブロモスクシンイミド(4.80g)を投入した。反応終了後、水を加え、分液洗浄した。有機相を無水硫酸ナトリウムで乾燥後、溶媒を留去して粗生成物を得た。これをTHFと酢酸エチルで洗浄して、生成物(5‐ブロモ‐5'‐ホルミル‐2,2'‐ビチオフェン、6.00g)を得た。 5-Formyl-2,2′-bithiophene (5.00 g) was dissolved in DMF (6 mL) and cooled to 0 ° C. N-bromosuccinimide (4.80 g) was added thereto. After completion of the reaction, water was added and the solution was separated and washed. The organic phase was dried over anhydrous sodium sulfate, and then the solvent was distilled off to obtain a crude product. This was washed with THF and ethyl acetate to give the product (5-bromo-5′-formyl-2,2′-bithiophene, 6.00 g).
5‐(5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル)チオフェン‐2‐カルバルデヒドの合成Synthesis of 5- (5- (4-hexylphenyl) thiophen-2-yl) thiophene-2-carbaldehyde
反応容器に、5‐ブロモ‐5'‐ホルミル‐2,2'‐ビチオフェン(5.52g)、2‐(4‐ヘキシルフェニル)‐4,4,5,5‐テトラメチル‐1,3,2‐ジオキサボロラン(6.23g)、10%炭酸ナトリウム水溶液(65mL)、ジオキサン(60mL)とキシレン(20mL)を加えて撹拌した。そこへテトラキストリフェニルホスフィンパラジウム(0.66g)を投入し、80℃に加温した。4時間加熱撹拌した後、クロロホルムと水を加えて分液洗浄した。有機相を無水硫酸ナトリウムで乾燥させ、溶媒を留去した。これをシリカゲルカラム(ヘキサン/クロロホルム=1/1→クロロホルム)で精製して、生成物(5‐(5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル)チオフェン‐2‐カルバルデヒド、5.40g)を得た。 To the reaction vessel, 5-bromo-5′-formyl-2,2′-bithiophene (5.52 g), 2- (4-hexylphenyl) -4,4,5,5-tetramethyl-1,3,2 -Dioxaborolane (6.23 g), 10% aqueous sodium carbonate solution (65 mL), dioxane (60 mL) and xylene (20 mL) were added and stirred. Tetrakistriphenylphosphine palladium (0.66 g) was added thereto and heated to 80 ° C. After stirring with heating for 4 hours, chloroform and water were added to separate and wash. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off. This was purified with a silica gel column (hexane / chloroform = 1/1 → chloroform) to give the product (5- (5- (4-hexylphenyl) thiophen-2-yl) thiophene-2-carbaldehyde, 5.40 g. )
5,10,15‐トリ[5‐[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリンの合成Synthesis of 5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin
ピロール(1.38g)、5‐(5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル)チオフェン‐2‐カルバルデヒド(5.40g)、テレフタルアルデヒド酸メチル(0.85g)をクロロホルム(150mL)とエタノール(2mL)に溶解させ、約10℃に冷却した。そこへ、三フッ化ホウ素(0.73g)を滴下し、そのまま2時間撹拌した。この溶液に、2,3‐ジクロロ‐5,6‐ジシアノ‐1,4‐ベンゾキノン(3.40g)を入れ、さらに1時間撹拌した。反応液をセライトとシリカゲルに通過させ、ろ液を濃縮して粗成生物を得た。これをシリカゲルカラム(クロロホルム)により展開分離し、生成物(5,10,15‐トリ[5‐[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン、0.40g)を得た。 Pyrrol (1.38 g), 5- (5- (4-hexylphenyl) thiophen-2-yl) thiophene-2-carbaldehyde (5.40 g), methyl terephthalaldehyde (0.85 g) in chloroform (150 mL) And ethanol (2 mL) and cooled to about 10 ° C. Thereto was added boron trifluoride (0.73 g) dropwise, and the mixture was stirred as it was for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (3.40 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column (chloroform), and the product (5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophen-2-yl] -20- ( 4-methoxycarbonylphenyl) porphyrin, 0.40 g) was obtained.
5,10,15‐トリ[5‐[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体の合成Synthesis of 5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex
5,10,15‐トリ[5‐[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン(0.40g)をクロロホルム(80mL)に溶解させた。そこへ、メタノール(20mL)に溶解させた酢酸亜鉛二水和物(0.45g)を滴下した。反応終了をTLCで確認後、水を加えて分液した。有機相を水で洗浄し、無水硫酸ナトリウムで乾燥させた。溶媒を留去し、粗成生物を得た。これをシリカゲルカラム(ヘキサン/クロロホルム=1/2→クロロホルム)で展開分離し、紫色生成物(5,10,15‐トリ[5‐[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体、0.20g)を得た。 5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin (0.40 g) in chloroform ( 80 mL). Thereto, zinc acetate dihydrate (0.45 g) dissolved in methanol (20 mL) was added dropwise. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column (hexane / chloroform = 1/2 → chloroform), and the purple product (5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophene was obtained. -2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex, 0.20 g).
5,10,15‐トリ[5‐[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]チオフェン‐2‐イル]‐20‐(4‐カルボキシルフェニル)ポルフィリン亜鉛(II)錯体(ポルフィリン誘導体P10)の合成5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophen-2-yl] -20- (4-carboxylphenyl) porphyrin zinc (II) complex (porphyrin derivative P10 )
5,10,15‐トリ[5‐[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]チオフェン‐2‐イル]‐20‐(4‐メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体(0.20g)をTHF(50mL)と水(30mL)に溶解させた。そこへ48%水酸化ナトリウム(3mL)を加え、原料が無くなるまで約68℃で加熱した。反応終了後、THFを留去した。残渣に3%ギ酸水を加え、弱酸性にした。クロロホルムで抽出し、有機相を水洗した。有機相を無水硫酸ナトリウムで乾燥させて溶媒を留去した。これをシリカゲルカラム(クロロホルム→クロロホルム/酢酸エチル=4/1)で精製して、紫色生成物(5,10,15‐トリ[5‐[5‐(4‐ヘキシルフェニル)チオフェン‐2‐イル]チオフェン‐2‐イル]‐20‐(4‐カルボキシルフェニル)ポルフィリン亜鉛(II)錯体、0.15g)を得た。
1H‐NMR(δH/ppm,THF,400MHz)0.92(t,9H),1.30‐1.40(m,18H),1.67(quin,6H),2.65(t,6H),7.25(d,6H),7.41(t,3H),7.45(t,3H),7.64(d,6H),7.70(t,3H),7.86(t,3H),8.31(d,2H),8.45(d,2H),8.86(d,2H),9.25(d,2H),9.27(s,4H)
5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] thiophen-2-yl] -20- (4-methoxycarbonylphenyl) porphyrin zinc (II) complex (0. 20 g) was dissolved in THF (50 mL) and water (30 mL). Thereto was added 48% sodium hydroxide (3 mL), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. Extraction was performed with chloroform, and the organic phase was washed with water. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off. This was purified with a silica gel column (chloroform → chloroform / ethyl acetate = 4/1) to give a purple product (5,10,15-tri [5- [5- (4-hexylphenyl) thiophen-2-yl] Thiophen-2-yl] -20- (4-carboxylphenyl) porphyrin zinc (II) complex, 0.15 g) was obtained.
1 H-NMR (δ H / ppm, THF, 400 MHz) 0.92 (t, 9H), 1.30-1.40 (m, 18H), 1.67 (quin, 6H), 2.65 (t , 6H), 7.25 (d, 6H), 7.41 (t, 3H), 7.45 (t, 3H), 7.64 (d, 6H), 7.70 (t, 3H), 7 .86 (t, 3H), 8.31 (d, 2H), 8.45 (d, 2H), 8.86 (d, 2H), 9.25 (d, 2H), 9.27 (s, 4H)
(ポルフィリン誘導体P11の合成)
5,10,15,20−テトラキス(4−メトキシカルボニルフェニル)−21H,23H−ポルフィリンの合成
(Synthesis of porphyrin derivative P11)
Synthesis of 5,10,15,20-tetrakis (4-methoxycarbonylphenyl) -21H, 23H-porphyrin
反応容器に、ピロール(1.48g)、テレフタルアルデヒド酸メチル(3.60g)、クロロホルム(600mL)とエタノール(9mL)を加えた。そこへ、三フッ化ホウ素(0.94g)を滴下し、そのまま2時間撹拌した。この溶液に、2,3‐ジクロロ‐5,6‐ジシアノ‐1,4‐ベンゾキノン(3.74g)を加え、さらに1時間撹拌した。反応液をセライトとシリカゲルに通過させ、ろ液を濃縮して粗成生物を得た。これをシリカゲルカラムで展開分離し、生成物(5,10,15,20−テトラキス(4−メトキシカルボニルフェニル)−21H,23H−ポルフィリン、0.45g)を得た。 To the reaction vessel, pyrrole (1.48 g), methyl terephthalaldehyde (3.60 g), chloroform (600 mL) and ethanol (9 mL) were added. Thereto was added boron trifluoride (0.94 g) dropwise, and the mixture was stirred for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (3.74 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated on a silica gel column to obtain a product (5,10,15,20-tetrakis (4-methoxycarbonylphenyl) -21H, 23H-porphyrin, 0.45 g).
5,10,15,20−テトラキス(4−メトキシカルボニルフェニル)−21H,23H−ポルフィリン(0.40g)をクロロホルム(50mL)に溶解させた。そこへ、メタノール(12ml)に溶解させた酢酸亜鉛二水和物(1.24g)を滴下した。反応終了をTLCで確認後、水を加えて分液した。有機相を水で洗浄し、無水硫酸ナトリウムで乾燥させた。溶媒を留去し、粗成生物を得た。これをシリカゲルカラムで展開分離し、紫色生成物(5,10,15,20−テトラキス(4−メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体、0.38g)を得た。
5,10,15,20−テトラキス(4−カルボキシフェニル)ポルフィリン亜鉛(II)錯体 (ポルフィリン誘導体P11)の合成
5,10,15,20-Tetrakis (4-methoxycarbonylphenyl) -21H, 23H-porphyrin (0.40 g) was dissolved in chloroform (50 mL). Thereto, zinc acetate dihydrate (1.24 g) dissolved in methanol (12 ml) was added dropwise. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column to obtain a purple product (5,10,15,20-tetrakis (4-methoxycarbonylphenyl) porphyrin zinc (II) complex, 0.38 g).
Synthesis of 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin zinc (II) complex (porphyrin derivative P11)
5,10,15,20−テトラキス(4−メトキシカルボニルフェニル)ポルフィリン亜鉛(II)錯体(0.35g)をTHF(35mL)と水(8mL)に溶解させた。そこへ48%水酸化ナトリウム(0.8g)を加え、原料が無くなるまで約68℃で加熱した。反応終了後、残渣に3%ギ酸水を加え、弱酸性にした。沈殿物を回収し、シリカゲルカラムで展開分離して、紫色生成物(5,10,15,20−テトラキス(4−カルボキシフェニル)ポルフィリン亜鉛(II)錯体 、0.29g)を得た。 5,10,15,20-Tetrakis (4-methoxycarbonylphenyl) porphyrin zinc (II) complex (0.35 g) was dissolved in THF (35 mL) and water (8 mL). Thereto was added 48% sodium hydroxide (0.8 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, 3% formic acid water was added to the residue to make it weakly acidic. The precipitate was recovered and developed and separated on a silica gel column to obtain a purple product (5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin zinc (II) complex, 0.29 g).
(ポルフィリン誘導体P12の合成)
5,10,15,20−テトラキス(4−メトキシフェニル)−21H,23H−ポルフィリンの合成
(Synthesis of porphyrin derivative P12)
Synthesis of 5,10,15,20-tetrakis (4-methoxyphenyl) -21H, 23H-porphyrin
反応容器に、p−メトキシフェニルジピロメタン(1.00g)、p−アニスアルデヒド(0.54g)とジクロロメタン(200mL)を加えた。そこへ、トリフルオロ酢酸(0.80g)を滴下し、1時間撹拌した。N,N−ジイソプロピルエチルアミン(0.90g)を加え、1時間撹拌した。この溶液に、p−クロラニル(1.48g)を加え、さらに2時間撹拌した。反応液をセライトとシリカゲルに通し、ろ液を濃縮して粗成生物を得た。これをシリカゲルカラムにより展開分離し、生成物(5,10,15,20−テトラキス(4−メトキシフェニル)−21H,23H−ポルフィリン、0.13g)を得た。 To the reaction vessel, p-methoxyphenyldipyromethane (1.00 g), p-anisaldehyde (0.54 g) and dichloromethane (200 mL) were added. Trifluoroacetic acid (0.80g) was dripped there and it stirred for 1 hour. N, N-diisopropylethylamine (0.90 g) was added and stirred for 1 hour. To this solution, p-chloranil (1.48 g) was added and further stirred for 2 hours. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column to obtain a product (5,10,15,20-tetrakis (4-methoxyphenyl) -21H, 23H-porphyrin, 0.13 g).
5,10,15,20−テトラキス(4−メトキシフェニル)ポルフィリン亜鉛(II)錯体 (ポルフィリン誘導体P12)の合成Synthesis of 5,10,15,20-tetrakis (4-methoxyphenyl) porphyrin zinc (II) complex (porphyrin derivative P12)
5,10,15,20−テトラキス(4−メトキシフェニル)−21H,23H−ポルフィリン(0.12g)をクロロホルム(30mL)に溶解させた。そこへ、メタノール(10mL)に溶解させた酢酸亜鉛二水和物(0.55g)を滴下した。反応終了をTLCで確認後、溶媒を留去し、粗成生物を得た。これをシリカゲルカラムで展開分離し、紫色生成物(5,10,15,20−テトラキス(4−メトキシフェニル)ポルフィリン亜鉛(II)錯体、0.08g)を得た。 5,10,15,20-Tetrakis (4-methoxyphenyl) -21H, 23H-porphyrin (0.12 g) was dissolved in chloroform (30 mL). Thereto, zinc acetate dihydrate (0.55 g) dissolved in methanol (10 mL) was added dropwise. After confirming the completion of the reaction by TLC, the solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column to obtain a purple product (5,10,15,20-tetrakis (4-methoxyphenyl) porphyrin zinc (II) complex, 0.08 g).
(ポルフィリン誘導体P15の合成)
5,10,15−トリ(4−メトキシカルボニルフェニル)−20−フェニルエチニル−21H,23H−ポルフィリンの合成
(Synthesis of porphyrin derivative P15)
Synthesis of 5,10,15-tri (4-methoxycarbonylphenyl) -20-phenylethynyl-21H, 23H-porphyrin
反応容器に、ピロール(0.66g)、テレフタルアルデヒド酸メチル(1.21g)、フェニルプロパギルアルデヒド(0.32g)、クロロホルム(500mL)とエタノール(7mL)を加えた。そこへ、三フッ化ホウ素(0.42g)を滴下し、そのまま2時間撹拌した。この溶液に、2,3‐ジクロロ‐5,6‐ジシアノ‐1,4‐ベンゾキノン(1.67g)を加え、さらに1時間撹拌した。反応液をセライトとシリカゲルに通過させ、ろ液を濃縮して粗成生物を得た。これをシリカゲルカラムにより展開分離し、生成物(5,10,15−トリ(4−メトキシカルボニルフェニル)−20−フェニルエチニル−21H,23H−ポルフィリン、0.16g)を得た。 To the reaction vessel, pyrrole (0.66 g), methyl terephthalaldehyde (1.21 g), phenylpropargylaldehyde (0.32 g), chloroform (500 mL) and ethanol (7 mL) were added. Thereto was added boron trifluoride (0.42 g) dropwise, and the mixture was stirred as it was for 2 hours. To this solution was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (1.67 g), and the mixture was further stirred for 1 hour. The reaction solution was passed through celite and silica gel, and the filtrate was concentrated to obtain a crude product. This was developed and separated by a silica gel column to obtain a product (5,10,15-tri (4-methoxycarbonylphenyl) -20-phenylethynyl-21H, 23H-porphyrin, 0.16 g).
5,10,15−トリ(4−メトキシカルボニルフェニル)−20−フェニルエチニルポルフィリン亜鉛(II)錯体の合成Synthesis of 5,10,15-tri (4-methoxycarbonylphenyl) -20-phenylethynylporphyrin zinc (II) complex
5,10,15−トリ(4−メトキシカルボニルフェニル)−20−フェニルエチニル−21H,23H−ポルフィリン(0.13g)をクロロホルム(20mL)に溶解させた。そこへ、メタノール(5mL)に溶解させた酢酸亜鉛二水和物(0.42g)を滴下した。反応終了をTLCで確認後、水を加えて分液した。有機相を水で洗浄し、無水硫酸ナトリウムで乾燥させた。溶媒を留去し、粗成生物を得た。これをシリカゲルカラムで展開分離し、紫色生成物(5,10,15−トリ(4−メトキシカルボニルフェニル)−20−フェニルエチニルポルフィリン亜鉛(II)錯体、0.11g)を得た。 5,10,15-tri (4-methoxycarbonylphenyl) -20-phenylethynyl-21H, 23H-porphyrin (0.13 g) was dissolved in chloroform (20 mL). Thereto, zinc acetate dihydrate (0.42 g) dissolved in methanol (5 mL) was added dropwise. After confirming the completion of the reaction by TLC, water was added to separate the layers. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product. This was developed and separated on a silica gel column to obtain a purple product (5,10,15-tri (4-methoxycarbonylphenyl) -20-phenylethynylporphyrin zinc (II) complex, 0.11 g).
5,10,15−トリ(4−カルボキシフェニル)−20−フェニルエチニルポルフィリン亜鉛(II)錯体 (ポルフィリン誘導体P15)の合成Synthesis of 5,10,15-tri (4-carboxyphenyl) -20-phenylethynylporphyrin zinc (II) complex (porphyrin derivative P15)
5,10,15−トリ(4−メトキシカルボニルフェニル)−20−フェニルエチニルポルフィリン亜鉛(II)錯体(0.10g)をTHF(12mL)と水(4mL)に溶解させた。そこへ48%水酸化ナトリウム(0.40g)を加え、原料が無くなるまで約68℃で加熱した。反応終了後、THFを留去した。残渣に3%ギ酸水を加え、弱酸性にした。沈殿物を回収し、シリカゲルカラムで展開分離して、紫色生成物(5,10,15−トリ(4−カルボキシフェニル)−20−フェニルエチニルポルフィリン亜鉛(II)錯体、0.06g)を得た。 5,10,15-tri (4-methoxycarbonylphenyl) -20-phenylethynylporphyrin zinc (II) complex (0.10 g) was dissolved in THF (12 mL) and water (4 mL). Thereto was added 48% sodium hydroxide (0.40 g), and the mixture was heated at about 68 ° C. until the raw material disappeared. After completion of the reaction, THF was distilled off. 3% aqueous formic acid was added to the residue to make it weakly acidic. The precipitate was collected and developed and separated on a silica gel column to obtain a purple product (5,10,15-tri (4-carboxyphenyl) -20-phenylethynylporphyrin zinc (II) complex, 0.06 g). .
(ポルフィリン誘導体P13およびP14)
5,10,15,20−テトラフェニル−21H,23H−ポルフィリン(ポルフィリン誘導体P13、CAS番号:917−23−7)は、和光純薬工業(株)から市販されているものを用いた。また、テトラキス(4−カルボキシフェニル)ポルフィリン(ポルフィリン誘導体P14,CAS番号:14609−54−2)は、東京化成工業(株)から市販されているものを用いた。
(Porphyrin derivatives P13 and P14)
As 5,10,15,20-tetraphenyl-21H, 23H-porphyrin (porphyrin derivative P13, CAS number: 917-23-7), one commercially available from Wako Pure Chemical Industries, Ltd. was used. Further, tetrakis (4-carboxyphenyl) porphyrin (porphyrin derivative P14, CAS number: 14609-54-2) used was commercially available from Tokyo Chemical Industry Co., Ltd.
3.比較化合物
比較例として、フタロシアニン亜鉛錯体(比較化合物Pc−a、CAS番号:13420−04−8、東京化成工業(株)製)および21H,23H−ポルフィリン(比較化合物Por−a、CAS番号:101−60−0、フナコシ(株)製)を用いた。
3. Comparative compounds As comparative examples, a phthalocyanine zinc complex (Comparative compound Pc-a, CAS number: 13420-04-8, manufactured by Tokyo Chemical Industry Co., Ltd.) and 21H, 23H-porphyrin (Comparative compound Por-a, CAS number: 101) -60-0, manufactured by Funakoshi Co., Ltd.).
4.有機色素複合体の合成
得られたフタロシアニン誘導体Aのエタノール溶液と、ポルフィリン誘導体P1のエタノール溶液を、下記実施例で設定したAとP1の混合比率および濃度となるように、25℃で混合した。
4). Synthesis of Organic Dye Complex The ethanol solution of the obtained phthalocyanine derivative A and the ethanol solution of porphyrin derivative P1 were mixed at 25 ° C. so as to have the mixing ratio and concentration of A and P1 set in the following examples.
5.有機色素複合体の評価
(紫外・可視吸収スペクトルの測定)
(a)二酸化チタン上に吸着された状態での紫外・可視吸収スペクトル測定
ガラス基板(フッ素ドープ酸化スズ膜形成ガラス、35mm×33mm)上に、二酸化チタンペースト(触媒化成製、PST−21NR)を、スクリーン印刷により正方形状(1cm×1cm、膜厚0.8μm)に印刷し、乾燥後、500℃で焼成した。形成された二酸化チタン膜を、フタロシアニン誘導体Aのエタノール溶液(0.1mmol/L)、ポルフィリン誘導体P1エタノール溶液(0.1mmol/L)、および有機色素複合体(A+P1)エタノール溶液(0.1mmol/L)に、それぞれ25℃で12時間浸漬した。浸漬後、該基板をエタノールで洗浄し、乾燥させ、紫外・可視吸収スペクトルを測定した。結果を図1(a)に示す。
(b)エタノール中での紫外・可視吸収スペクトル測定
フタロシアニン誘導体A、ポルフィリン誘導体P1、および有機色素複合体A+P1のそれぞれ5μmol/Lエタノール溶液を調整し、紫外・可視吸収スペクトルを測定した。結果を図1(b)に示す。
5. Evaluation of organic dye complexes (measurement of ultraviolet and visible absorption spectra)
(A) Ultraviolet / visible absorption spectrum measurement in a state of being adsorbed on titanium dioxide On a glass substrate (fluorine-doped tin oxide film-forming glass, 35 mm × 33 mm), a titanium dioxide paste (catalyst conversion, PST-21NR) is applied. Then, it was printed in a square shape (1 cm × 1 cm, film thickness 0.8 μm) by screen printing, dried, and fired at 500 ° C. The formed titanium dioxide film was subjected to ethanol solution (0.1 mmol / L) of phthalocyanine derivative A, porphyrin derivative P1 ethanol solution (0.1 mmol / L), and organic dye complex (A + P1) ethanol solution (0.1 mmol / L). L) for 12 hours at 25 ° C., respectively. After immersion, the substrate was washed with ethanol, dried, and the ultraviolet / visible absorption spectrum was measured. The results are shown in FIG.
(B) Ultraviolet / visible absorption spectrum measurement in ethanol A 5 μmol / L ethanol solution of each of phthalocyanine derivative A, porphyrin derivative P1 and organic dye complex A + P1 was prepared, and an ultraviolet / visible absorption spectrum was measured. The results are shown in FIG.
図1(a)および図1(b)のいずれにおいても、吸収スペクトルの長波長シフトが観測された。 In both FIG. 1 (a) and FIG. 1 (b), a long wavelength shift of the absorption spectrum was observed.
(有機色素複合体の会合定数の測定)
Rose−Drago法(非特許文献2参照)に従い、エタノール溶液中での有機色素複合体(A+P1)の会合定数を測定した。結果を表2に示す。
(Measurement of association constant of organic dye complex)
According to the Rose-Drago method (see Non-Patent Document 2), the association constant of the organic dye complex (A + P1) in an ethanol solution was measured. The results are shown in Table 2.
表2に示すとおり、有機色素複合体(A+P1)は、非常に大きな会合定数を有する会合体を形成していることがわかった。 As shown in Table 2, it was found that the organic dye complex (A + P1) formed an association having a very large association constant.
(有機色素複合体を濃度変化させた場合の紫外・可視吸収スペクトルの測定)
上記有機色素複合体(A+P1)の溶液濃度を1.25μmol/L、2.5μmol/L、5.μmol/L、10μmol/L、20μmol/L、および30μmol/Lに変化させ、それぞれの溶液の紫外・可視吸収スペクトルを測定した。結果を図3に示す。
(Measurement of ultraviolet and visible absorption spectrum when the concentration of organic dye complex is changed)
4. Solution concentration of the organic dye complex (A + P1) is 1.25 μmol / L, 2.5 μmol / L, It changed to micromol / L, 10 micromol / L, 20 micromol / L, and 30 micromol / L, and the ultraviolet and visible absorption spectrum of each solution was measured. The results are shown in FIG.
図3のとおり、有機色素複合体(A+P1)は、濃度1.25μmol/Lの極低濃度であっても一部に会合体を形成していることがわかった。 As shown in FIG. 3, it was found that the organic dye complex (A + P1) partially formed an aggregate even at an extremely low concentration of 1.25 μmol / L.
(フタロシアニン誘導体とポルフィリン誘導体との混合比率を変化させた場合の紫外・可視吸収スペクトルの測定)
上記有機色素複合体(A+P1)の合成において、フタロシアニン誘導体Aとポルフィリン誘導体P1との混合比率を変えて調整し、得られた溶液の紫外・可視吸収スペクトルを測定した。結果を図4に示す。
(Measurement of ultraviolet and visible absorption spectra when the mixing ratio of phthalocyanine derivative and porphyrin derivative is changed)
In the synthesis of the organic dye complex (A + P1), the mixture was adjusted by changing the mixing ratio of the phthalocyanine derivative A and the porphyrin derivative P1, and the ultraviolet / visible absorption spectrum of the obtained solution was measured. The results are shown in FIG.
図4のとおり、本発明の有機色素複合体(A+P1)は混合比率1:9〜9:1の範囲で、その一部が会合体を形成していることがわかった。 As shown in FIG. 4, it was found that the organic dye complex (A + P1) of the present invention partly formed an aggregate in the mixing ratio range of 1: 9 to 9: 1.
(種々の有機色素複合体の形成)
上記有機色素複合体(A+P1)と同様に、フタロシアニン誘導体A〜Dまたは比較化合物Pc−aと、ポルフィリン誘導体P1〜P15または比較化合物Por−aとを1:1の比率で混合し、有機色素複合体または有機色素混合物の5μmol/Lエタノール溶液を作成した。その結果を表3および図5に示す。該溶液中での会合体の形成の有無は、フタロシアニン誘導体およびポルフィリン誘導体を1:1で混合した際に、用いたフタロシアニン誘導体単独の最大吸収スペクトルを基準に、当該波長の吸収スペクトルがフタロシアニン誘導体単独の場合の90%以下となり、その長波長側に新たな吸収波長が観察された場合に、会合体が形成されたものと判断した。
(Formation of various organic dye complexes)
Similar to the organic dye complex (A + P1), the phthalocyanine derivatives A to D or the comparative compound Pc-a and the porphyrin derivatives P1 to P15 or the comparative compound Por-a are mixed at a ratio of 1: 1 to obtain the organic dye complex. A 5 μmol / L ethanol solution of the body or organic dye mixture was prepared. The results are shown in Table 3 and FIG. The presence or absence of the formation of the aggregate in the solution is determined based on the absorption spectrum of the wavelength when the phthalocyanine derivative and the porphyrin derivative are mixed at 1: 1, based on the maximum absorption spectrum of the phthalocyanine derivative used alone. When the absorption wavelength was 90% or less and a new absorption wavelength was observed on the longer wavelength side, it was determined that an aggregate was formed.
表3および図5から明らかなように、比較例5〜7では、フタロシアニン誘導体およびポルフィリン誘導体のそれぞれの吸収スペクトルが単に重なり合っただけであり、会合体の吸収スペクトルは観測されなかった。 As is apparent from Table 3 and FIG. 5, in Comparative Examples 5 to 7, the respective absorption spectra of the phthalocyanine derivative and porphyrin derivative merely overlapped, and the absorption spectrum of the aggregate was not observed.
(色素増感太陽電池の作製)
(1)以下の手順により、上記合成例により調製した有機色素複合体(A+P1:実施例1)ならびにフタロシアニン誘導体A単独およびポルフィリン誘導体P1単独を用いた色素増感太陽電池をそれぞれ作製した。
(Preparation of dye-sensitized solar cell)
(1) Dye-sensitized solar cells using the organic dye complex (A + P1: Example 1) prepared in the above synthesis example, and the phthalocyanine derivative A alone and the porphyrin derivative P1 alone were prepared by the following procedure.
i. ガラス基板(フッ素ドープ酸化スズ膜形成ガラス、35mm×33mm)上に、
二酸化チタンペースト(触媒化成製、PST−21NR)を、スクリーン印刷により正方形状(1cm×1cm、膜厚8μm)に印刷し、乾燥後、その上にさらに二酸化チタンペースト(触媒化成製、PST−400C)を膜厚4μmにスクリーン印刷した。これを500℃で焼成し、発電層を形成した。
i. On a glass substrate (fluorine-doped tin oxide film-formed glass, 35 mm × 33 mm),
Titanium dioxide paste (catalyst conversion, PST-21NR) is printed in a square shape (1 cm × 1 cm, film thickness 8 μm) by screen printing, dried, and then further titanium dioxide paste (catalyst conversion, PST-400C). ) Was screen printed to a film thickness of 4 μm. This was baked at 500 ° C. to form a power generation layer.
ii. 前記発電層を形成した電極をフタロシアニン誘導体Aのエタノール溶液(0.1mmol/L)、ポルフィリン誘導体P1エタノール溶液(0.1mmol/L)、および有機色素複合体(A+P1)エタノール溶液(0.1mmol/L)に、それぞれ25℃で12時間浸漬した。浸漬後、該基板をエタノールで洗浄し、乾燥させ、アノード電極を得た。 ii. The electrode on which the power generation layer was formed was prepared by using an ethanol solution of phthalocyanine derivative A (0.1 mmol / L), a porphyrin derivative P1 ethanol solution (0.1 mmol / L), and an organic dye complex (A + P1) ethanol solution (0. 1 mmol / L) at 25 ° C. for 12 hours. After immersion, the substrate was washed with ethanol and dried to obtain an anode electrode.
iii. 上記アノード電極の発電層の周囲に接着剤を施し、このアノード電極と、別途用意した電解液注入孔を有するチオアセトアミドで処理した白金被覆チタン板(カソード電極)とを、該接着剤により接着し、両電極が50μm程度の一定間隔を置いて平行に配置されるようにした。 iii. Adhesive is applied around the power generation layer of the anode electrode, and the anode electrode and a platinum-coated titanium plate (cathode electrode) treated with thioacetamide having a separately prepared electrolyte injection hole are bonded with the adhesive. The electrodes were bonded so that both electrodes were arranged in parallel at a constant interval of about 50 μm.
iv. 次いで、該電解液注入口より電解液を注入した。ここで、電解液には、ヨウ素(0.1molM/L)、ヨウ化リチウム(0.1mol/L)、1−プロピル−3−メチルイミダゾリウムヨウ化物(0.8mol/L)、およびN−メチルベンゾイミダゾール(0.5mol/L)が、それぞれカッコ内に記載した濃度になるように3−メトキシプロピオニトリルに添加された溶液を用いた。 iv. Next, an electrolytic solution was injected from the electrolytic solution injection port. Here, the electrolyte includes iodine (0.1 molM / L), lithium iodide (0.1 mol / L), 1-propyl-3-methylimidazolium iodide (0.8 mol / L), and N- A solution in which methylbenzimidazole (0.5 mol / L) was added to 3-methoxypropionitrile so as to have the concentration described in parentheses was used.
v. 接着剤を用いて該電解液注入孔を封止し、アノード電極上に端子取り出しのためのハンダを塗布して実験用セルを完成させた。 v. The electrolyte injection hole was sealed with an adhesive, and solder for terminal removal was applied onto the anode electrode to complete the experimental cell.
(分光感度の測定)
作製した太陽電池セルの分光感度を分光感度測定装置(分光計器株式会社製CEP−2000)で測定した。結果を図6に示す。また、これらの太陽電池セルの外観を図7に示す。
(Measurement of spectral sensitivity)
The spectral sensitivity of the produced solar battery cell was measured with a spectral sensitivity measuring device (CEP-2000 manufactured by Spectrometer Co., Ltd.). The results are shown in FIG. Moreover, the external appearance of these photovoltaic cells is shown in FIG.
(性能試験)
上記のようにして得られた色素増感太陽電池につきその性能を評価した。
(performance test)
The performance of the dye-sensitized solar cell obtained as described above was evaluated.
セルを作成後、該セルを庫内温度85℃の乾燥機(ヤマト科学株式会社製 DK810)内に設置した。24時間後セルを取り出し室温まで冷却した後、AM1.5,1SUN(100mW/cm2)の照射条件下でセルの変換効率を測定した。結果を表4に示す。 After creating the cell, the cell was placed in a dryer (DK810, manufactured by Yamato Scientific Co., Ltd.) having an internal temperature of 85 ° C. After 24 hours, the cell was taken out and cooled to room temperature, and then the conversion efficiency of the cell was measured under irradiation conditions of AM 1.5, 1 SUN (100 mW / cm 2 ). The results are shown in Table 4.
なお光電変換効率は下記式により計算した。
光電変換効率(%)=
100×[(短絡電流密度×開放電圧×曲線因子)/(照射太陽光エネルギー)]
The photoelectric conversion efficiency was calculated by the following formula.
Photoelectric conversion efficiency (%) =
100 × [(Short-circuit current density × Open circuit voltage × Curve factor) / (Irradiated solar energy)]
上記表4のとおり、本発明の有機色素複合体を光増感色素として用いて作製した色素増感太陽電池は、高い光電変換効率を示した。これは、図6で明らかなように、本発明の有機色素複合体が、構成するフタロシアニン誘導体およびポルフィリン誘導体の吸収波長の単なる和とは異なる、より長波長側に広がった吸収波長を有することから、より広い範囲の光を吸収することができ、光電変換効率が向上したものと考えられる。 As shown in Table 4 above, the dye-sensitized solar cell produced using the organic dye composite of the present invention as a photosensitizing dye showed high photoelectric conversion efficiency. This is because, as is apparent from FIG. 6, the organic dye complex of the present invention has an absorption wavelength that extends to the longer wavelength side, which is different from the mere sum of the absorption wavelengths of the phthalocyanine derivative and porphyrin derivative. It is considered that a wider range of light can be absorbed and the photoelectric conversion efficiency is improved.
1 透明電極
2 金属酸化物半導体電極
3 電解質
4 対電極
DESCRIPTION OF SYMBOLS 1 Transparent electrode 2 Metal oxide semiconductor electrode 3 Electrolyte 4 Counter electrode
Claims (7)
X1〜X8はOであり、n1〜n8はそれぞれ独立して0または1であり、
M1はフタロシアニンと結合しうる任意の少なくとも1つの原子または原子団を表す)
で表されるフタロシアニン誘導体またはその塩と、
以下の一般式(2)
M2はポルフィリンと結合しうる任意の少なくとも1つの原子または原子団を表す)
で表されるポルフィリン誘導体またはその塩との複合体。 The following general formula (1)
X 1 to X 8 are O, n 1 to n 8 are each independently 0 or 1,
M 1 represents any at least one atom or atomic group capable of binding to phthalocyanine)
A phthalocyanine derivative represented by
The following general formula (2)
M 2 represents any at least one atom or atomic group capable of binding to porphyrin)
A porphyrin derivative represented by the formula: or a complex thereof.
X1〜X8はOであり、n1〜n8はそれぞれ独立して0または1であり、
M1はフタロシアニンと結合しうる任意の少なくとも1つの原子または原子団を表す)
で表されるフタロシアニン誘導体またはその塩と、
以下の一般式(2)
M2はポルフィリンと結合しうる任意の少なくとも1つの原子または原子団を表す)
で表されるポルフィリン誘導体またはその塩と
を液体媒体中で混合することを含む複合体の製造方法。 The following general formula (1)
X 1 to X 8 are O, n 1 to n 8 are each independently 0 or 1,
M 1 represents any at least one atom or atomic group capable of binding to phthalocyanine)
A phthalocyanine derivative represented by
The following general formula (2)
M 2 represents any at least one atom or atomic group capable of binding to porphyrin)
A method for producing a complex comprising mixing a porphyrin derivative represented by the formula (I) or a salt thereof in a liquid medium.
X1〜X8はOであり、n1〜n8はそれぞれ独立して0または1であり、
M1はフタロシアニンと結合しうる任意の少なくとも1つの原子または原子団を表す)
で表されるフタロシアニン誘導体またはその塩と、
以下の一般式(2)
M2はポルフィリンと結合しうる任意の少なくとも1つの原子または原子団を表す)
で表されるポルフィリン誘導体またはその塩と
の複合体を含む太陽電池用光増感色素。 The following general formula (1)
X 1 to X 8 are O, n 1 to n 8 are each independently 0 or 1,
M 1 represents any at least one atom or atomic group capable of binding to phthalocyanine)
A phthalocyanine derivative represented by
The following general formula (2)
M 2 represents any at least one atom or atomic group capable of binding to porphyrin)
The photosensitizing dye for solar cells containing the composite_body | complex with the porphyrin derivative represented by these, or its salt.
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