CN103261191A - 萘单酰亚胺衍生物及其在太阳能电池和光电检测器中作为光敏剂的用途 - Google Patents
萘单酰亚胺衍生物及其在太阳能电池和光电检测器中作为光敏剂的用途 Download PDFInfo
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- CN103261191A CN103261191A CN2011800617434A CN201180061743A CN103261191A CN 103261191 A CN103261191 A CN 103261191A CN 2011800617434 A CN2011800617434 A CN 2011800617434A CN 201180061743 A CN201180061743 A CN 201180061743A CN 103261191 A CN103261191 A CN 103261191A
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- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title description 8
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 125000001072 heteroaryl group Chemical group 0.000 claims description 17
- -1 alkali metal cation Chemical group 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000004414 alkyl thio group Chemical group 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 125000004104 aryloxy group Chemical group 0.000 claims description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 7
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 125000005110 aryl thio group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 3
- 125000005368 heteroarylthio group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 238000010572 single replacement reaction Methods 0.000 claims description 2
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 claims 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000007787 solid Substances 0.000 description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000011541 reaction mixture Substances 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- 239000000975 dye Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 11
- 239000004327 boric acid Substances 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 150000001335 aliphatic alkanes Chemical group 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 229930192474 thiophene Natural products 0.000 description 7
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004873 anchoring Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 238000007872 degassing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001235 sensitizing effect Effects 0.000 description 5
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000010511 deprotection reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 3
- 125000001544 thienyl group Chemical group 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229920001651 Cyanoacrylate Polymers 0.000 description 2
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 125000005266 diarylamine group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000001906 matrix-assisted laser desorption--ionisation mass spectrometry Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
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- GKLMJONYGGTHHM-UHFFFAOYSA-N 1-bromo-4-hexoxybenzene Chemical compound CCCCCCOC1=CC=C(Br)C=C1 GKLMJONYGGTHHM-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
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- DJRKHTCUXRGYEU-UHFFFAOYSA-N 4-Hexyloxyaniline Chemical compound CCCCCCOC1=CC=C(N)C=C1 DJRKHTCUXRGYEU-UHFFFAOYSA-N 0.000 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RYXZOQOZERSHHQ-UHFFFAOYSA-N [2-(2-diphenylphosphanylphenoxy)phenyl]-diphenylphosphane Chemical compound C=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1OC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RYXZOQOZERSHHQ-UHFFFAOYSA-N 0.000 description 1
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000999 acridine dye Substances 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- IDLFZVILOHSSID-OVLDLUHVSA-N corticotropin Chemical compound C([C@@H](C(=O)N[C@@H](CO)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC=1NC=NC=1)C(=O)N[C@@H](CC=1C=CC=CC=1)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)NCC(=O)N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](C(C)C)C(=O)NCC(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CC=1C=CC(O)=CC=1)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CC(N)=O)C(=O)NCC(=O)N[C@@H](C)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CO)C(=O)N[C@@H](C)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C)C(=O)N[C@@H](CC=1C=CC=CC=1)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(O)=O)NC(=O)[C@@H](N)CO)C1=CC=C(O)C=C1 IDLFZVILOHSSID-OVLDLUHVSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
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- 238000007598 dipping method Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- YUAUWEGVKKQBNY-UHFFFAOYSA-N n-hexoxyaniline Chemical compound CCCCCCONC1=CC=CC=C1 YUAUWEGVKKQBNY-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000005412 pyrazyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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Abstract
提供式Ia和Ib的化合物,其中变量R、n、A、B、R1和R2各自如说明书中所定义。还公开了式Ia或Ib化合物或其混合物和/或其异构体或异构体混合物作为太阳能电池和光电检测器中的光敏剂的用途。还提供了包含该式Ia或Ib化合物或其混合物和/或其异构体或异构体混合物作为光敏剂的太阳能电池和光电检测器。
Description
发明描述
本发明涉及式Ia和Ib的化合物:
其中
R为相同或不同的芳氧基、芳硫基、杂芳氧基或杂芳硫基,
n为0、1、2、3、4或5,
B为C1-C6亚烷基或1,4-亚苯基,其中所述亚苯基可被烷基、硝基、氰基和/或卤素单取代或多取代,
A为-COOM、-SO3M或-PO3M,
M为氢、碱金属阳离子或[NR′]4 +,
R′为氢或烷基,其中基团R′可相同或不同,
L为下式的桥基:
—Ar—,—Ar—Ar—或—Ar—Ar—Ar—
其可被苯基、烷基、烷氧基、烷硫基和/或-NR4R5单取代或多取代,且其中Ar为可与饱和或不饱和的5-18员环稠合的芳基或杂芳基,所述5-18员环可包含杂原子,在2个或3个Ar的情况下,其可相同或不同,
R4、R5各自独立地为氢,其碳链可被一个或多个-O-、-S-、-CO-、-SO-和/或-SO2-结构部分间隔的烷基,芳基或杂芳基,其各自可被烷基、烷氧基和/或烷硫基单取代或多取代,
R1、R2各自独立地为式IIa或IIb的基团:
R3为苯基、烷基、烷氧基、烷硫基或-NR7R8,
m为0、1、2、3或4,
X为C(R6R7)2、NR8、氧或硫,且
R6、R7、R8各自独立地为氢,其碳链可被一个或多个-O-、-S-、-CO-、-SO-和/或-SO2-结构部分间隔的烷基,芳基或杂芳基,其各自可被烷基、烷氧基和/或烷硫基单取代或多取代。
本发明进一步涉及式Ia或Ib化合物或式Ia和Ib化合物的混合物和/或式Ia和Ib化合物的异构体或异构体混合物作为太阳能电池和光电检测器中的光敏剂的用途,以及包含该式Ia或Ib化合物或式Ia和Ib化合物的混合物和/或式Ia和Ib化合物的异构体或异构体混合物作为光敏剂的太阳能电池和光电检测器。
在太阳能电池中太阳能直接转化成电能基于半导体材料的内光电效应,即通过吸收光子产生电子-空穴对并在p-n结或肖特基触点处分离负载流子和正载流子。由此产生的光电压可在外部电路中产生光电流,借此太阳能电池输送电力。
半导体仅可吸收能量高于其带隙的那些光子。因此,半导体带隙的大小决定了可转化成电能的阳光比例。
已知金属氧化物薄层或膜为廉价的固体半导体材料(n型半导体),然而由于大的带隙,其吸收通常不处于电磁波谱的可见区。因此,为了用于太阳能电池中,金属氧化物必须与在阳光的波长范围(即300-2000nm)内吸收并在电子激发态下将电子注入半导体的导带中的光敏剂组合。借助额外用于所述电池中且在对电极处还原的氧化还原体系,电子再循环至敏化剂中,由此使得其再生。
特别令人感兴趣的用于太阳能电池中的为以纳米晶体多孔层形式使用的半导体氧化锌、二氧化锡,和尤其是二氧化钛。这些层具有被敏化剂涂覆的大表面积,从而获得阳光的高吸收率。
基于二氧化钛作为半导体材料的染料敏化太阳能电池描述于例如US-A-4927721;Nature353,第737-740页(1991)以及US-A-5350644和Nature395,第583-585页(1998)和EP-A-1176646中。这些太阳能电池包括过渡金属配合物,尤其钌配合物(其经由酸基键至二氧化钛层)的单分子膜作为光敏剂以及以溶解形式存在的碘/碘化物氧化还原体系或基于螺双芴的无定形有机p型导体。
也出于成本原因,还反复提议使用不含金属的有机染料作为敏化剂。
日本文献JP-A-10-189065、2000-243463、2001-093589、2000-100484和10-334954以及New J.Chem.26,第1155-1160页(2002)研究了作为敏化剂的苝-3,4:9,10-四甲酸衍生物。然而,基于这些苝衍生物的液体电解质太阳能电池显示出比用于对照的用钌配合物敏化的太阳能电池低得多的效率。
目前最广泛研究的敏化剂包括具有氰基丙烯酸酯锚固基团的染料。例如Kim,S.;Lee,J.K.;Kang,S.O.;Yum,j.H.;Fantacci,S.;DeAngelis,F.;Di Censo,D.;Nazeerruddin,M.K.;M.JACS2006,128,16701研究了如下化合物:
且Solar Energy Materials&Solar Cells2009,93,1143研究了如下化合物:
然而,根据Solar Energy Materials&Solar Cells2009,93,1143,所述氰基丙烯酸酯锚固基团不够稳定;发现这些染料脱羧并怀疑所述锚固基团对光不稳定。
具有萘单酰亚胺锚固基团的染料描述于文献WO2008/132103A1中,然而这些化合物在阳光的短波光谱区域内吸收(绝对最大值位于约450nm处),因此不适于有效吸收并转化阳光。
现已令人惊讶地发现包含萘单酰亚胺基团作为锚固基团的本发明式Ia和Ib化合物显示出良好至非常好的量子效率且在染料太阳能电池中具有非常好的稳定性。
因此,发现了开头所详述的式Ia和Ib化合物及其作为太阳能电池和光电检测器中的光敏剂的用途。
就本发明而言,芳基为芳族基团、单元或基,尤其是具有6-30个碳原子,优选6-18个碳原子的基础骨架且由一个芳族环或多个稠合芳族环形成的基团。合适的基础骨架例如为苯基、苄基、萘基、蒽基或菲基。该基础骨架可为未取代的(这意味着所有可取代的碳原子均带有氢原子)或在所述基础骨架的一个、多于一个或所有可取代位置上被取代。合适的取代基例如为烷基,优选具有1-8个碳原子的烷基,更优选甲基、乙基、异丙基或叔丁基;芳基,优选C6芳基,其又可被取代或未被取代;杂芳基,优选包含至少一个氮原子的杂芳基,更优选吡啶基;链烯基,优选具有一个双键的链烯基,更优选具有一个双键和1-8个碳原子的链烯基;或者具有供体或受体作用的基团。具有供体作用的基团应理解为意指具有+I和/或+M效应的基团,具有受体作用的基团应理解为意指具有-I和/或-M效应的基团。具有给体或受体作用的合适基团为卤素基团,优选F、Cl、Br,更优选F;烷基、烷氧基、芳氧基、羰基、酯基、胺基、酰胺基、CH2F基、CHF2基、CF3基、CN基、硫基或SCN基。所述芳族基团或芳基最优选具有选自甲基、乙基、异丙基、正丙基、正丁基、异丁基、叔丁基、芳氧基、胺基、硫基和烷氧基的取代基,或者所述芳基未被取代。所述芳基优选为任选被至少一个上述取代基取代的苯基。所述苯基更优选具有0、1、2或3个上述取代基。
就本发明而言,杂芳基为杂芳族基团、单元或基,其为具有5-30个,优选具有5-18个碳原子和/或杂原子且与上述芳基的不同之处在于芳基的基础骨架中的至少一个碳原子被杂原子代替的基团。优选的杂原子为N、O和S。最优选地,所述芳基的基础骨架的一个或两个碳原子被杂原子代替。尤其优选所述基础骨架选自如下体系,如吡啶基、嘧啶基、吡唑基(pyrazyl)和三唑基,以及5元杂芳族化合物如吡咯、呋喃、噻吩、咪唑、吡唑、三唑、唑和噻唑。所述基础骨架可在该基础骨架的一个、多于一个或所有可取代位置上被取代。合适的取代基与已对所述芳基提及的相同。
就本发明而言,芳氧基、芳硫基、杂芳氧基和杂芳硫基在形式上由上述芳基和杂芳基通过在所述芳基或杂芳基的碳原子上连接氧原子或硫原子而衍生。
就本发明而言,烷基为烷烃基团、单元或基,尤其是具有1-20个碳原子,优选1-12个碳原子的基团。该烷基可为支化或未支化的,且任选被一个或多个-O-、-S-、-CO-、-SO-和/或-SO2-结构部分间隔。烷基更优选选自甲基、乙基、异丙基、正丙基、异丁基、正丁基、叔丁基、仲丁基、异戊基、正戊基、仲戊基、新戊基、正己基、异己基和仲己基。
就本发明而言,烷氧基和烷硫基在形式上由上述烷基通过在所述烷基的碳原子上连接氧原子或硫原子而衍生。
就本发明而言,卤素优选为F、Cl或Br,更优选F。
就本发明而言,碱金属阳离子优选为Li、Na、Cs或K,更优选Na。
当桥基L被苯基、烷基、烷氧基、烷硫基和/或-NR4R5单取代或多取代时,这意味着这些取代基连接在芳族或杂芳族Ar基团的合适位置上。
当桥基L包含2或3个Ar时,其可相同或不同。
合适的Ar实例包括1,4-、1,3-和1,2-亚苯基;1,4-和1,8-亚萘基;1,4-和2,3-亚吡咯基(pyrrylen);2,5-、2,4-和2,3-亚噻吩基;2,5-、2,4-和2,3-亚呋喃基;2,3-、2,4-、2,5-、2,6-、3,4-和3,5-亚吡啶基;2,3-、2,5-、2,6-、3,7-、4,8-、5,8-和6,7-亚喹啉基;2,7-、3,6-、4,5-、2,6-、3,7-、4,7-和4,8-亚异喹啉基;1,4-(2,5-二叔丁基)亚苯基;1,4-(2,5-二己基)亚苯基;1,4-(2,5-二叔辛基)亚苯基;1,4-(2,5-双十二烷基)亚苯基和1,4-[2,5-二(2-十二烷基)]亚苯基。作为Ar尤其有用的是1,4-亚苯基和2,5-亚噻吩基。
合适的桥基L例如为:
优选:
优选为如下本发明化合物,其中在式Ia和Ib中:
R为相同或不同的芳氧基或芳硫基,尤其为苯氧基或苯硫基,
n为0、1或2,
B为C1-C6亚烷基,尤其为-CH2-、-(CH2)2-和-(CH2)3-,
A为-COOM,
M为氢或碱金属阳离子,
L为下式的桥基:
—Ar—Ar—或—Ar—Ar—Ar—
其可被苯基、C1-C12烷基、C1-C12烷氧基、C1-C12烷硫基和/或-NR4R5单取代或多取代,且其中Ar为相同或不同的可与饱和或不饱和的5-18员环稠合的芳基或杂芳基,所述5-18员环可包含杂原子,
R4、R5各自独立地为氢,其碳链可被一个或多个-O-、-S-、-CO-、-SO-和/或-SO2-结构部分间隔的C1-C12烷基,
R1、R2各自独立地为式II′a和II′b的基团:
R3为C1-C12烷氧基,
m为0或1,
X为C(R6R7)2、NR8、氧或硫,且
R6、R7、R8各自独立地为氢,其碳链可被一个或多个-O-、-S-、-CO-、-SO-和/或-SO2-结构部分间隔的C1-C12烷基。
特别优选如下本发明化合物,其中在式Ia和Ib中:
n为0,
B为C1-C6亚烷基,尤其为-CH2-和-(CH2)2-,
A为-COOM,
M为氢或碱金属阳离子,
L为下式的桥基:
—Ar—Ar—或—Ar—Ar—Ar—,
其中Ar为相同或不同的芳基或杂芳基,
R1、R2各自独立地为式II′a和II′b的基团:
R3为C1-C12烷氧基,
m为0或1,
X为C(R6R7)2,且
R6、R7各自独立地为氢或C1-C12烷基。
本发明应不仅涵盖式Ia和Ib的化合物及其优选实施方案,而且涵盖其混合物、其异构体和异构体的混合物。
例如,本发明还涵盖如下所示的式I*b的异构化合物:
实施例
实施例1:
由(4-溴苯基)双(9,9-二甲基-9H-芴-2-基)胺起始制备(根据Ko等,Chemical Communications,2004,68-69),首先使其与噻吩-2,5-二硼酸酯反应(步骤a):
此后,与N-(2-羧乙基)-4-氯代萘酰亚胺的甲酯偶合并使酯基脱保护(步骤b)。
步骤a):
在氮气下将1.66g(2.98mmol)(4-溴苯基)双(9,9-二甲基-9H-芴-2-基)胺、2.00g(5.96mmol)噻吩-2,5-二硼酸酯、溶于5.2mL10:1H2O/乙醇中的0.82g(5.96mmol)K2CO3、92mg(0.06mmol)Pd(PPh3)4和10mL甲苯的混合物加热至85°C,并在该温度下搅拌4小时。
冷却后,将所述反应混合物吸滤。母液通过与二氯甲烷/H2O振摇萃取。从有机相中除去溶剂并干燥残留物。粗产物未经提纯即用于下一反应步骤。
步骤b):
将2.00g步骤a的粗产物、1.33g(4.38mmol)N-(2-羧乙基)-4-氯代萘酰亚胺的甲酯、50.4mg(0.055mmol)Pd2(dba)3、1.43g(4.38mmol)Cs2CO3、26.3mg(0.13mmol)三丁基膦和二烷的混合物加热至90°C,并在该温度下搅拌6小时。冷却后,将所述反应混合物吸滤,然后从母液中除去溶剂。粗产物通过柱层析使用正己烷/乙酸乙酯(2:1)提纯。获得70mg受保护的化合物。
将后者在60°C下与处于10mL1:1软化水:THF中的200mg KOH一起搅拌1天。冷却后,添加10mL浓HCl并将所述混合物搅拌1小时。然后将所述反应混合物添加至软化水中。吸滤出固体,用热的软化水洗涤并干燥。
通过柱层析使用洗脱液10:1二氯甲烷:乙醇+2%三甲胺进行提纯。通过在60°C下与50%乙酸一起搅拌而提取所得的固体,吸滤并用热的软化水洗涤。干燥后获得1.2g红色固体。
分析数据:
1H NMR(500MHz,CDCl3,25°C):δ=8.79(d,1H);8.68(d,1H);8.63(d,1H);7.88(d,1H);7.80(q,1H),7.66(d,2H);7.63(d,2H);7.58(d,2H);7.40(t,3H);7.33(m,3H);7.27(m,4H);7.23(d,2H);7.15(d,2H);5.02(s,2H);1.43(s,12H)
实施例2:
由(4-溴苯基)双(9,9-二甲基-9H-芴-2-基)胺起始制备(根据Ko等,Chemical Communications,2004,68-69),首先使其与2,2-双噻吩-5-硼酸酯反应(步骤a)。随后溴化(步骤b),然后与下式结构的4-硼酸酯萘酰亚胺偶合:
并使酯基脱保护(步骤c)。
步骤a:
用氩气将1.67g(3.00mmol)(4-溴苯基)双(9,9-二甲基-9H-芴-2-基)胺、1.80mL(9.00mmol)5M NaOH和10mL二烷的混合物脱气30分钟。然后添加54mg(0.160mmol)Pd[P(tBu)3]2和1.00g(3.42mmol)2,2-双噻吩-5-硼酸酯:
并将所述混合物加热至85°C并搅拌整个周末。冷却后,将所述反应混合物添加至冰水中。随后,用二氯甲烷萃取并从有机相中除去溶剂。将残留物溶于少许四氢呋喃中。向其中添加甲醇直至固体沉淀出。吸滤出后者,用少许甲醇洗涤并干燥。获得1.40g黄色固体,这对应于73%的产率。
分析数据:
1H NMR(500MHz,DMSO,25°C):δ=7.77(m,4H);7.62(d,2H);7.51(d,3H);7.41(d,1H);7.31(m,8H);7.11(m,3H);7.05(d,2H);1.37(s,12H)
步骤b:
在0-5°C下,将466mg(2.62mmol)N-溴代琥珀酰亚胺和10mL DMF溶液滴加至1.40g(2.18mmol)步骤a与20mL二甲基甲酰胺(DMF)的混合物中。然后在该温度下继续搅拌15分钟,然后添加10mL硫代硫酸钠稀溶液。将所述反应混合物添加至150mL软化水中并用甲基叔丁基醚(MTBE)萃取。从有机相中除去溶剂并干燥残留物。获得1.20g黄色固体,这对应于76%的产率。
分析数据:
1H NMR(500MHz,DMSO,25°C):δ=7.77(m,4H);7.62(d,2H);7.51(d,2H);7.42(d,1H);7.31(m;7H);7.23(d,1H);7.17(d,1H);7.11(d,2H);7.06(d,1H);1.37(s,12H)
步骤c:
用氩气将1.00g(1.4mmol)步骤b、0.84mL(4.2mmol)5M NaOH和15mL二烷的混合物脱气30分钟。然后添加24mg(0.05mmol)Pd[P(tBu)3]2和0.97g(1.6mmol)上文所示的4-硼酸酯萘酰亚胺(65%),并将所述混合物加热至85°C并搅拌1天。冷却后,将所述反应混合物添加至冰水中并用二氯甲烷萃取。从有机相中除去溶剂。残留物借助柱层析使用洗脱液4:1二氯甲烷:甲醇提纯。
获得了受保护的目标产物,将其与1:1THF:水和1g KOH在65°C下搅拌过夜。冷却后,将所述反应混合物添加至水中,并加入15mL浓HCl。将所述混合物在室温下搅拌1小时。然后吸滤出固体、并将其洗涤并干燥。粗产物借助柱层析使用洗脱液4:1二氯甲烷:甲醇提纯。这获得330mg红色固体,对应于26%的产率。
分析数据:
1H NMR(500MHz,DMSO,25°C):δ=8.80(d,1H);8.61(d,1H);8.55(d,1H);7.99(q,2H);7.76(g,4H);7.65(d,2H);7.55(q,2H);7.51(d,2H);7.47(d,2H);7.30(m,6H);7.12(d,2H);7.06(d,2H);4.75(s,2H);1.34(s,12H)
实施例3:
由二芳基胺起始制备,首先使其与双噻吩-5-硼酸酯反应(步骤a)。随后溴化(步骤b),然后与2-硼酸酯萘酰亚胺偶合(步骤c)。
步骤a:
用氩气将1.80g(2.9mmol)二芳基胺、15mL二烷和1.74mL(8.7mmol)5M NaOH的混合物脱气30分钟。然后添加51mg(0.1mmol)Pd[P(tBu)3]2和0.91g(3.11mmol)双噻吩-5-硼酸酯,并将所述混合物加热至85°C并搅拌整个周末。冷却后,将所述反应混合物添加至冰水中并用二氯甲烷萃取。从有机相中除去溶剂,并将残留物溶于少许THF中并加入甲醇。吸滤出沉淀的固体并干燥。借助柱层析使用洗脱液正己烷+2%乙酸乙酯进行提纯。这获得1.70g黄色固体,对应于85%的产率。
分析数据:
1H NMR(500MHz,DMSO,25°C):δ=7.41(d,4H);7.34(d,2H);7.26(d,1H);7.14(d,1H);7.08(d,1H);7.04(d,1H);6.99(d,2H);6.86(d,3H);6.81(d,2H);6.76(d,2H);6.65(d,2H);3.56(s,6H);1.11(s,12H)
步骤b:
在0-5°C下,将490mg(2.40mmol)N-溴代琥珀酰亚胺和10mL DMF溶液滴加至1.6g(2.3mmol)步骤a与30mL DMF的混合物中。然后在该温度下继续搅拌15分钟,然后添加10mL硫代硫酸钠稀溶液。将所述反应混合物添加至150mL软化水中。吸滤出固体、并使其洗涤并干燥。获得1.62g黄色固体,这对应于90%的产率。
分析数据:
1H NMR(500MHz,DMSO,25°C):δ=7.66(d,4H);7.58(d,2H);7.40(d,1H);7.30(d,1H);7.26(d,2H);7.23(d,1H);7.16(d,1H);7.11(d,2H);7.07(d,2H);7.01(d,2H);6.90(d,2H);3.81(s,6H);1.36(s,12H)
步骤c:
用氩气将1.00g(1.3mmol)步骤b、0.78mL(3.9mmol)5M NaOH和15mL二烷的混合物脱气30分钟。然后添加26mg(0.05mmol)Pd[P(tBu)3]2和0.59g(1.5mmol)的下式化合物:
并将所述混合物加热至85°C并搅拌1天。冷却后,将所述反应混合物添加至冰水中并用二氯甲烷萃取。从有机相中除去溶剂。残留物借助柱层析使用洗脱液4:1二氯甲烷:甲醇提纯两次。这获得630mg红色固体,对应于68%的产率。
分析数据:
1H NMR(500MHz,DMSO,25°C):δ=8.75(d,1H);8.58(d,1H);8.51(d,1H);7.96(m,2H);7.65(d,4H);7.62(d,2H);7.53(s,2H);7.45(s,2H);7.26(d,2H);7.11(d,2H);7.07(d,2H);7.02(d,2H);6.90(d,2H);4.51(s,2H);3.81(s,6H);1.36(s,12H)
实施例4:
由4-己氧基溴苯起始制备,使其与对己氧基苯胺反应(步骤a)。使所得的胺进一步与1,4-二溴苯反应(步骤b)。随后与2,2-双噻吩-5-硼酸酯偶合(步骤c)并溴化(步骤d)。最后,用2-硼酸酯萘酰亚胺进行偶合并使酯基脱保护(步骤e)。
步骤a:
将20g(78mmol)4-己氧基苯胺、18g(93mmol)对己氧基溴苯、0.87g(3.9mmol)乙酸钯(II)、3.1g(5.8mmol)DPEphos、12g(125mmol)叔丁醇钠和100mL甲苯的混合物加热至100°C并搅拌1天。冷却后,从所述反应混合物中除去溶剂。粗产物借助柱层析使用洗脱液2:1二氯甲烷:己烷提纯。获得19.7g白色固体,这对应于68%的产率。
分析数据:
1H NMR(500MHz,CD2Cl2,25°C):δ=6.91(d,4H);6.79(d,4H);5.35(s,1H);3.90(t,4H);1.74(m,4H);1.45(m,4H);1.34(m,8H);0.91(t,6H);
步骤b:
将5.4g(14.6mmol)步骤a、6.9g(29.2mmol)1,4-二溴苯、275mg(0.30mmol)Pd2(dba)3、405mg(0.73mmol)DPPF、2.80g(29.2mmol)叔丁醇钠和40mL甲苯的混合物加热至90°C并搅拌2天。冷却后,从所述反应混合物中除去溶剂。借助柱层析使用洗脱液4:1己烷:二氯甲烷进行提纯。获得5.6g浅色油,这对应于72%的产率。
分析数据:
1H NMR(500MHz,DMSO,25°C):δ=7.29(d,2H);6.99(d,4H);6.89(d,4H);6.66(d,2H);3.92(t,4H);1.69(m,4H);1.40(m,4H);1.30(m,8H);0.88(t,6H)
步骤c:
用氩气将1.6g(3.1mmol)步骤b、15mL二烷和1.86mL(9.3mmol)5MNaOH的混合物脱气30分钟。然后添加51mg(0.11mmol)Pd[P(tBu)3]2和0.98g(3.31mmol)2,2-双噻吩-5-硼酸酯,并将所述混合物加热至85°C并搅拌整个周末。冷却后,将所述反应混合物添加至冰水中并用二氯甲烷萃取。从有机相中除去溶剂。借助柱层析使用洗脱液正己烷+2%乙酸乙酯进行提纯。这获得1.62g黄色固体,对应于86%的产率。
分析数据:
1H NMR(500MHz,DMSO,25°C):δ=7.48(m,3H);7.30(m,2H);7.25(d,1H);7.09(q,1H);7.03(q,4H);6.92(q,4H);6.76(q,2H);3.94(t,4H);1.70(m,4H);1.41(m,4H);1.31(m,8H);0.88(t,6H)
步骤d:
在0-5°C下,将430mg(2.40mmol)N-溴代琥珀酰亚胺和10mL DMF的溶液滴加至1.2g(2.00mmol)步骤c和30mL DMF的混合物中。然后在该温度下继续搅拌15分钟,然后添加10mL硫代硫酸钠稀溶液。将所述反应混合物添加至150mL软化水中并用MTBE萃取,从有机相中除去溶剂。获得1.0g黄色固体,这对应于73%的产率。
分析数据:
1H NMR(500MHz,DMSO,25°C):δ=7.46(d,2H);7.29(d,1H);7.27(d,1H);7.21(d,1H);7.14(d,1H);7.03(d,4H);6.92(d,4H);6.75(d,2H);3.94(t,4H);1.70(m,4H);1.41(m,4H);1.31(m,8H);0.98(t,6H)
步骤e:
用氩气将0.90g(1.3mmol)步骤d、0.78mL(3.9mmol)5M NaOH和15mL二烷的混合物脱气30分钟。然后添加22mg(0.04mmol)Pd[P(tBu)3]2和0.91g(1.5mmol)下式化合物:
并将所述混合物加热至85°C并搅拌1天。冷却后,将所述反应混合物添加至冰水中并用二氯甲烷萃取,从有机相中除去溶剂。残留物借助柱层析使用洗脱液4:1二氯甲烷:甲醇+1%三乙胺提纯两次。获得受保护的目标产物,将其与1:1THF:水和1g KOH在65°C下搅拌过夜。冷却后,将所述反应混合物添加至水中,并加入15mL浓HCl。将所述混合物在室温下搅拌1小时。然后用二氯甲烷萃取所述混合物,然后从有机相中除去溶剂。粗产物借助柱层析使用洗脱液4:1二氯甲烷:甲醇+2%三乙胺提纯。这获得610mg红色固体,对应于54%的产率。
分析数据:
1H NMR(500MHz,DMSO,25°C):δ=8.78(d,1H);8.60(d,1H);8.53(d,1H);7.97(m,2H);7.53(m,4H);7.41(d,1H);7.34(d,1H);7.03(d,4H);6.92(d,4H);6.77(d,2H);4.72(s,2H);3.93(t,4H);1.70(m,4H);1.41(m,4H);1.31(m,8H);0.88(t,6h)
实施例5(以异构体5a和5b的混合物存在的化合物):
将[4-(5'-溴-[2,2']双噻吩-5-基)苯基]双(9,9-二甲基-9H-芴-2-基)胺(450mg,0.62mmol)溶于二烷(15ml)中,添加5MNaOH(0.4mL,1.9mmol)并用氩气将所述混合物脱气30分钟。然后引入Pd[P(tBu)3]2(10mg,0.02mmol)和6-(4,4,5,5-四甲基-[1,3,2]二氧杂硼烷-2-基)苯并[去]异苯并吡喃-1,3-二酮(330mg,1mmol),并将所述混合物在85°C下搅拌过夜。冷却后,将所述混合物添加至冰水中并用二氯甲烷萃取,浓缩有机相。这获得490mg橙色固体。
Maldi-MS:M+=837.27
将6-(5'-{4-[双-(9,9-二甲基-9H-芴-2-基)氨基]苯基[2,2']双噻吩-5-基)-苯并[去]异苯并吡喃-1,3-二酮(400mg,0.48mmol)、乙酸锌(88mg,0.22mmol)和3,4-二氨基苯甲酸(220mg,1.44mmol)引入喹啉(40ml)中。将所述混合物加热至220°C并搅拌7小时。冷却后,用6%HCl进行沉淀并吸滤出固体,用热水和少许乙醇洗涤。用5:1二氯甲烷:甲醇进行柱层析,获得98mg(21%)橙色固体。
Maldi-MS:M+=953.24
应用实施例:
所用的衬底为涂覆有氟掺杂的氧化锡(FTO)且尺寸为25mm×15mm×3mm的玻璃板(Nippon Sheet Glass),其依次用玻璃清洁剂(RBS35)、软化水和丙酮处理,在每种情况下在超声浴中处理5分钟,然后在异丙醇中煮沸10分钟并在氮气气流中干燥。
为了制备固体TiO2阻挡层,使用如Peng等,Coord.Chem.Rev.248(2004),1479所述的喷雾热解法。以丝网印刷法将TiO2糊DSL18NR-T(Dyesol)印刷至所述固体TiO2阻挡层上。所述糊由分散于松油醇/乙基纤维素混合物中的直径为约25nm的TiO2颗粒构成。在该印刷工艺之后,将所述糊在80°C下干燥5分钟。随后在450°C下烧结30分钟。所得纳孔TiO2层的层厚为1.8μm。
除了所述TiO2层,为了在金属背电极和工作电极之间电绝缘,可将聚酰亚胺带(Pyrolin Polyimide Coating,Supelco)沿各纵向侧放置并在干燥箱中于200°C下固化15分钟。
从干燥箱中取出后,将试样冷却至80°C,在5×10-4M羟肟酸盐的乙醇溶液(所述盐通过使市售羟肟酸与氢氧化钠溶液反应而获得)中浸渍16小时,
然后取出,用EtOH简单洗涤,然后置于5×10-4M的处于二氯甲烷中的本发明染料溶液或对照化合物JK2溶液中1小时。随后用纯溶剂(此处为二氯甲烷)漂洗从所述溶液中取出的试样并在氮气流中干燥。
将p型导体溶液旋涂至所述干燥的试样上。所述溶液由如下物质构成:处于氯苯中的0.16M螺-MeOTAD(Merck)和处于环己酮中的0.3MLiN(SO2CF3)2(Aldrich)(二者之比为15:1)以及基于螺-MeOTAD为2.5重量%的V2O5。将125μl该溶液施加至试样上并使其作用60秒。随后,在2000rpm下旋除过量溶液达30秒。
通过在减压下热金属蒸发而施加金属背电极。为此,为所述试样提供掩膜以将尺寸为0.13cm2的8个分离的背电极施加至活性区域。为此,在约5*10-5毫巴压力下以3.0-3.5nm/s速率蒸发Ag,从而获得200nm的层厚。
量子效率(IPCE=入射光子/电流转换效率)使用75瓦氙弧光灯(LOT-Oriel)、1/8m单色仪(SpectraPro-2150i;Acton Research Corporation)、互阻抗放大器(Aescusoft GmbH Automation)和锁相放大器(lock-inamplifier)(信号复原)测定。
电流/电压特性在100mW/cm2照射强度(具有AM1.5滤色片的氙灯(LOT-Oriel))下通过使电压在-0.6V和+1.0V之间变化并测量所得短路电流而获得。不同的本发明化合物和现有技术化合物JK2的数据示于表1(ISC:短路电流,VOC:开路电压;FF:填充因子;ETA:效率)。
表1
染料 | Isc[mA/cm2] | Voc[mV] | FF[%] | ETA[%] |
2a | -7.8 | 820 | 63 | 3.9 |
4a | -7.5 | 840 | 61 | 3.8 |
3a | -7.4 | 840 | 59 | 3.6 |
3a(甲苯)* | -7.7 | 860 | 64 | 4.1 |
5a/b | -7.8 | 900 | 42 | 2.9 |
JK2 | -9.2 | 860 | 58 | 4.6 |
*:“3a(甲苯)”意指所述染料不像通常那样由二氯甲烷溶液施加,而是由甲苯溶液施加。
图1显示了作为波长函数的本发明化合物和现有技术化合物JK2的EQE值。
图2显示了化合物2a的本发明染料与现有技术染料JK2的耐光性对比,在每种情况下,位于TiO2上。照射系列在日光测试仪中“光浸泡(lightsoaking)”2小时后开始。
图3显示了作为时间函数的具有染料2a的短路太阳能电池效率。为了测定该效率,使用100mW/cm2(具有AM1.5滤色片的氙灯(LOT-Oriel))的功率照射,在Source Meter型号2400(Keithley Instruments Inc.)中记录电流/电压特性。
Claims (5)
1.式Ia或Ib的化合物:
其中
R为相同或不同的芳氧基、芳硫基、杂芳氧基或杂芳硫基,
n为0、1、2、3、4或5,
B为C1-C6亚烷基或1,4-亚苯基,其中所述亚苯基可被烷基、硝基、氰基和/或卤素单取代或多取代,
A为-COOM、-SO3M或-PO3M,
M为氢、碱金属阳离子或[NR′]4 +,
R′为氢或烷基,其中基团R′可相同或不同,
L为下式的桥基:
-Ar-,-Ar-Ar-或-Ar-Ar-Ar-
其可被苯基、烷基、烷氧基、烷硫基和/或-NR4R5单取代或多取代,且其中Ar为可与饱和或不饱和的5-18员环稠合的芳基或杂芳基,所述5-18员环可包含杂原子,在2个或3个Ar的情况下,其可相同或不同,
R4、R5各自独立地为氢,其碳链可被一个或多个-O-、-S-、-CO-、-SO-和/或-SO2-结构部分间隔的烷基,芳基或杂芳基,其各自可被烷基、烷氧基和/或烷硫基单取代或多取代,
R1、R2各自独立地为式IIa或IIb的基团:
R3为苯基、烷基、烷氧基、烷硫基或-NR7R8,
m为0、1、2、3或4,
X为C(R6R7)2、NR8、氧或硫,且
R6、R7、R8各自独立地为氢,其碳链可被一个或多个-O-、-S-、-CO-、-SO-和/或-SO2-结构部分间隔的烷基,芳基或杂芳基,其各自可被烷基、烷氧基和/或烷硫基单取代或多取代。
2.根据权利要求1的化合物,其中在式Ia和Ib中,
R为相同或不同的芳氧基或芳硫基,
n为0、1或2,
B为C1-C6亚烷基,
A为-COOM,
M为氢或碱金属阳离子,
L为下式的桥基:
-Ar-Ar-或-Ar-Ar-Ar-
其可被苯基、C1-C12烷基、C1-C12烷氧基、C1-C12烷硫基和/或-NR4R5单取代或多取代,且其中Ar为相同或不同的可与饱和或不饱和5-18员环稠合的芳基或杂芳基,所述5-18员环可包含杂原子,
R4、R5各自独立地为氢,其碳链可被一个或多个-O-、-S-、-CO-、-SO-和/或-SO2-结构部分间隔的C1-C12烷基,
R1、R2各自独立地为下式II′a和II′b的基团:
R3为C1-C12烷氧基,
m为0或1,
X为C(R6R7)2、NR8、氧或硫,且
R6、R7、R8各自独立地为氢或其碳链可被一个或多个-O-、-S-、-CO-、-SO-和/或-SO2-结构部分间隔的C1-C12烷基。
4.根据权利要求1、2或3的式Ia或Ib化合物或式Ia和Ib化合物的混合物和/或根据权利要求1、2或3的式Ia和Ib化合物的异构体或异构体混合物在太阳能电池和光电检测器中作为光敏剂的用途。
5.一种太阳能电池或光电检测器,包含根据权利要求1、2或3的式Ia或Ib化合物或式Ia和Ib化合物的混合物和/或根据权利要求1、2或3的式Ia和Ib化合物的异构体或异构体混合物作为光敏剂。
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