WO2009053107A1 - Squarylium dyes including an anchoring group - Google Patents
Squarylium dyes including an anchoring group Download PDFInfo
- Publication number
- WO2009053107A1 WO2009053107A1 PCT/EP2008/009074 EP2008009074W WO2009053107A1 WO 2009053107 A1 WO2009053107 A1 WO 2009053107A1 EP 2008009074 W EP2008009074 W EP 2008009074W WO 2009053107 A1 WO2009053107 A1 WO 2009053107A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dye
- scheme
- conjugated system
- formula
- represented
- Prior art date
Links
- 239000000975 dye Substances 0.000 title claims abstract description 357
- 238000004873 anchoring Methods 0.000 title claims abstract description 39
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 24
- 239000004065 semiconductor Substances 0.000 claims description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000001044 red dye Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000005859 coupling reaction Methods 0.000 claims description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 14
- 230000008878 coupling Effects 0.000 claims description 13
- 238000010168 coupling process Methods 0.000 claims description 13
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000007832 transition metal-catalyzed coupling reaction Methods 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 6
- 229910006069 SO3H Inorganic materials 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical class OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910018828 PO3H2 Inorganic materials 0.000 claims description 3
- 238000010511 deprotection reaction Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 2
- 229910003204 NH2 Inorganic materials 0.000 claims 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 54
- 239000000243 solution Substances 0.000 description 41
- 239000000203 mixture Substances 0.000 description 39
- 239000000654 additive Substances 0.000 description 32
- 230000000996 additive effect Effects 0.000 description 32
- 239000011248 coating agent Substances 0.000 description 30
- 238000000576 coating method Methods 0.000 description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 description 20
- 229960003964 deoxycholic acid Drugs 0.000 description 20
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 13
- 230000001443 photoexcitation Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229910052707 ruthenium Inorganic materials 0.000 description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 230000005283 ground state Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 229940093499 ethyl acetate Drugs 0.000 description 5
- 235000019439 ethyl acetate Nutrition 0.000 description 5
- 230000005281 excited state Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical group OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 4
- 0 C=C1C(C2*CC2)(*=[Cn])c2cc(C3CCCCC3)ccc2*1*1CC1 Chemical compound C=C1C(C2*CC2)(*=[Cn])c2cc(C3CCCCC3)ccc2*1*1CC1 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 238000000302 molecular modelling Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 238000003306 harvesting Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium dioxide Chemical compound O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KGPQKNJSZNXOPV-UHFFFAOYSA-N moniliformin Chemical class OC1=CC(=O)C1=O KGPQKNJSZNXOPV-UHFFFAOYSA-N 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000004424 polypyridyl Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- VLSRKCIBHNJFHA-UHFFFAOYSA-N 2-(trifluoromethyl)prop-2-enoic acid Chemical group OC(=O)C(=C)C(F)(F)F VLSRKCIBHNJFHA-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- FNYUJNATUMEWIU-UHFFFAOYSA-N B(O)O.C(=O)C=1SC=CC1 Chemical compound B(O)O.C(=O)C=1SC=CC1 FNYUJNATUMEWIU-UHFFFAOYSA-N 0.000 description 1
- 229910002913 BO2 Inorganic materials 0.000 description 1
- 229910018572 CuAlO2 Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VELDYOPRLMJFIK-UHFFFAOYSA-N O=CC1CCCC1 Chemical compound O=CC1CCCC1 VELDYOPRLMJFIK-UHFFFAOYSA-N 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JPBGLQJDCUZXEF-UHFFFAOYSA-N chromenylium Chemical compound [O+]1=CC=CC2=CC=CC=C21 JPBGLQJDCUZXEF-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125851 compound 27 Drugs 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004984 smart glass Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- DFNPRTKVCGZMMC-UHFFFAOYSA-M tributyl(fluoro)stannane Chemical compound CCCC[Sn](F)(CCCC)CCCC DFNPRTKVCGZMMC-UHFFFAOYSA-M 0.000 description 1
- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/007—Squaraine dyes
-
- 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
- H01G9/2063—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution comprising a mixture of two or more dyes
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/652—Cyanine dyes
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- 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
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- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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- 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
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- Y02E10/549—Organic PV cells
Definitions
- M Sn(alkyl) 3 , B(OR) 2 , MgHaI, ZnR 2 , R being in this case an H or any alkyl group, preferably a C
- the device according to the present invention further comprises at least one other dye.
- the dye in accordance with the present invention and said at least one other dye are mixed.
- the dye in accordance with the present invention and said at least one other dye are not on or in separate layers each, but rather being chemisorbed to one photoactive semiconductor layer.
- said at least one other dye is red-dye or black-dye or a combination of the two.
- the device according the present invention comprises a semiconductor porous material, preferably with one or several of the following specifications.
- - semiconductor porous material can be TiO 2 , SnO 2 , ZnO, Nb 2 O 5 , ZrO 2 , CeO 2 , WO 3 , Cr 2 O 3 , CrO 2 , CrO 3 , SiO 2 , Fe 2 O 3, CuO, Al 2 O 3 , CuAlO 2 , SrTiO 3, SrCu 2 O 2 , ZrTiO4
- the device may possibly be a photovoltaic device containing a charge-transporting agent which can be a liquid, polymer gel based or solid state electrolyte.
- a charge-transporting agent which can be a liquid, polymer gel based or solid state electrolyte.
- the dye molecules are adsorbed to the nanoporous particles via self-assembling out of a dye solution or a dyes-mixture solution.
- figure 1 shows an example of a synthesis scheme of one embodiment of a dye according to the present invention, wherein a halogenated chromophore is reacted with a metalated conjugated system comprising a carboxyaldehyde moiety in its structure, and thereafter the car- boxyaldehyde moiety is transformed into an anchoring group,
- figure 5 shows an example of a synthesis scheme of one embodiment according to the present invention, wherein an intermediate, the halogenated squarylium dye of general formula 1 is produced,
- figure 13 shows various embodiments of electronic devices in accordance with the present invention which include energy supply devices, such as DSSC panels, in accordance with the present invention.
- Step b) A mixture of compound 4 and cyano acrylic acid in acetonitrile are heated in the presence of small amount of piperidine to 80°C for 12 hours. After cooling, the solvent is removed under reduced pressure and the crude product is purified by column chromatography on silica gel with (5/5) acetone/ ethylacetate to give the dye 5 as a green red shining powder.
- UV/VIS (acetonitrile): ⁇ max 645 nm.
- the anchoring group is believed to be responsible for the efficient adsorption of the dye-sensitizer onto the nanoporous semiconductor surface and consist of an acrylic acid moiety which is optionally bridged by a conjugated system to the main core of the dye. This kind of anchoring group is believed to enable a photo-excitation induced intramolecular electron density relocation in organic dyes resulting in better performance of the sensitizer in a photovoltaic device.
- IPCE incident photon to current efficiency
- Example 16 Efficiency of M-DSSC containing the organic sensitizer dye 24 and 5 prepared by the method described in Example 6b and measured according to Example 7b. For comparison also DSSCs with the respective single sensitizer dye were prepared and measured.
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Abstract
The present invention relates to squarylium dyes including an anchoring group, to a method of synthesis of such dye, to an electronic device comprising such dye, and to uses of such dye.
Description
Squarylium dyes including an anchoring group
The present invention relates to squarylium dyes including an anchoring group in their structure, to a method of synthesis of such dyes, to an electronic device comprising such dyes, and to uses of such dyes.
The dye-sensitised solar cell (DSSC) (B. O'Regan and M. Gratzel, Nature 353 (1991) 737; WO 91/16719 [A]) is a photovoltaic device that offers high energy-conversion efficiencies at low cost. In contrast to the silicon-based systems, where the semiconductor assumes both the task of light absorption and charge carrier transport, in DSSCs these functions are separated. Light is absorbed by a sensitizer dye which is anchored to the surface of a semiconductor such as nanocrystalline TiO2. The charge separation takes place at the interface via photo-induced electron injection from the dye into the conduction band of the semiconductor. The dye molecule is regenerated from a counter electrode via a redox couple in the electrolyte. The redox couple is regenerated in turn at the counter-electrode the circuit being completed by electron transport through the external load.
The efficiency of a DSSC is determined by the number of collected and injected photons, and thus by the light absorbed by the dye sensitizer. For high efficiencies, the ideal sensitizer should absorb efficiently over a broad range of solar spectrum. In addition, for efficient electron injection it must be able to adsorb (by chemisorption) onto the semiconductor surface. Upon photo-excitation it should inject electrons into the conduction band of the semiconductor with a quantum yield of unity. To minimize energy losses during electron transfer, the energy level of its excited state should be well matched with the lower bound of the conduction band of the semiconductor. Its redox potential should be well matched with that of the redox couple so that the dye regeneration via electron donation is possible.
The best photovoltaic performance has so far been achieved with carboxyl groups containing polypyridyl complexes of ruthenium (known as red-dye and black-dye).[l] The photoexcita- tion of a Ru-complex results in an intramolecular metal-to-ligand charge-transfer (MLCT) transition. The photoexcited electrons located in the bipyridyl ligands can be very efficiently injected in the conduction band of the semiconductor via the carboxyl-anchor groups. This process has been shown to be very fast. [2] In contrast, for these complexes the recombination process between the injected electrons in TiO2 and the dye-cations is a slow process. The slow recombination is considered to be a result of the large separation between semiconductor and
the Ru3+ by the bipyridyl ligands. Thus, the molecular design of these Ru-complexes is successful in an efficient charge separation and thus, high energy conversion efficiency. However, the energy conversion efficiency of the DSSC is limited by the light-harvesting capacity of these Ru-dyes to absorb the sunlight. The photo-active region of the photovoltaic device is reduced to the visible part of the solar spectrum, and within that, to the shorter wavelength region. The photons of the longer wavelength region are not harvested and cannot be converted to electrical energy.
To improve the overall light to electricity conversion efficiency of a solar cell the photo- response has to be extended in the longer wavelength region of the solar spectrum. Thus, new dyes with absorption bands above 600 nm are required. The synthetic modification of the commonly employed ruthenium complexes towards this goal is limited.
It is therefore desirable to develop new organic dyes which have several advantages as photo- sensitizers: a) they have intense absorption (high extinction coefficients 10-100 higher than Ru-complexes), such that little material is needed for harvesting lot of light; b) their physical properties are amenable to being modified / tuned by chemical structural modification; c) they are cheaper since they don't contain metals, such as ruthenium.
However, to achieve as high efficiencies with organic dyes as achieved with polypyridyl Ru- complexes, sophisticated molecular design as described above for the Ru-complexes is required. Although, many organic dyes such as coumarin, merocyanine and polyene dyes have already been developed for DSSCs, most dyes reported so far absorb light in the same range as the commonly used red-dye (below 600 nm).[3] Thus, photons of the longer wavelength region are still lost to photoconversion.
Accordingly, it was an object of the present invention to provide for new dyes to be used in dye-sensitized solar cells. Moreover, it was an object of the present invention to provide for easy accessible, stable and soluble functional materials with intense absorption in the visible and long wavelength region of the solar spectrum. Moreover, it was an object of the present invention to provide for photostable dyes which have intense absorption with absorption coefficients > 105 L mol 1 cm"1 in the visible and IR-region of the solar spectrum. It was also an object of the present invention to provide for dyes which may be combined with other dyes so as to cover a broad range of the solar spectrum and thereby collect light over a broad range thereof. Moreover, it was an object of the present invention to provide for dyes whose band- gap and energy levels can be tuned and which can be efficiently chemisorbed to the nanopor-
ous surface of a photoactive layer. It was also an object of the present invention to provide for an improved dye to be used in dye-sensitized solar cells.
Noticeable is the fact that there are some organic dyes with good efficiencies reported that have an acrylic acid group attached. [5] However, as said before, they absorb light only in the range of the red dye. The dyes reported in the present application are capable to absorb the light also in the longer wavelength region.
The objects of the present invention are solved by a dye represented by formula I
(formula I)
G being an anchoring group, said anchoring group allowing a covalent coupling of said dye to a surface, for example a surface of a nanoporous semiconductor layer, said anchoring group being selected from -COOH, -SO3H, -PO3H2, -BO2H2, -SH, -OH, -NH2, preferably -COOH,
wherein A is selected from the group comprising H, -CN, -NO2, -COOR, -COSR, -COR, - CSR, -NCS, -CF3, -CONR2,-OCF3, C6H5-mFm, wherein m = 1 - 5, preferably -CN or -CF3, R being H or any straight or branched alkyl chain of general formula -CnH2n+i, n = 0-12, preferably 0-4,
wherein R31, R32, R33, R34, R3s, R36 , at each occurrence, are independently selected from H or any straight or branched chain of general formula -(CH2)nCH3, -(CH2)n-COOR, (CH2)n-OR, -
(CH2)n-SR, -(CH2VNR2, -((CH2VO)n-CH3, n = O - 12, preferably 0-6, and p= 1 -4, R being as defined above, or any substituted or non-substituted phenyl or biphenyl,
wherein said conjugated system is represented by a moiety shown in formula II
(formula II)
or a combination of any of the moieties represented by formula II,
wherein n\ and n2 = 0 - 12, preferably ni = 0-3 and n2 = 1 -7, wherein R3 is selected from
H, -(CH2)nCH3, -(CH2)n-COOR, -(CH2)n-OR, -(CH2)n-SR,
-(CH2VNR2, -((CH2)P-O)n-CH3, p= 1-4, n = 0-12, R being as defined above, and wherein Ri is selected from halogen, such as Cl, Br, F, I, Or NO2, NH2, CN, SO3H, OH, H, -(CH2)nCH3, -(CH2)n-COOR,
-(CH2)n-OR, -(CH2)n-SR, -(CH2)n-NR2, -((CH2)P-O)n-CH3, p= 1-4, n = 0-12,
R being as defined above.
In one embodiment the dye according to the present invention is able to absorb in the wavelength range of visible and/or IR light, preferably in the range from 300-1200 nm, or a subrange thereof, preferably 580-850 nm
In one embodiment the dye according to the present invention has the formula III
(CH2)n-SR, -(CHo)n-NR2, -((CH2VO)n-CH3, n = 0 - 12, preferably 0-6, and p= 1 -4, R being as defined above, or any substituted or non-substituted phenyl or biphenyl,
A, Ri and n2 being as described above
In one embodiment the dye according to the present invention has the formula IV
(formula IV)
wherein R3i, R32, R33, R34, R35, R36 , at each occurrence, are independently selected from H or any straight or branched chain of general formula -(CH2)nCH3, -(CH2)n-COOR, -(CH2)n-OR, -
(CH2)n-SR, -(CH2)n-NR2, -((CH2)P-O)n-CH3, n = 0 - 12, preferably 0-6, and p= 1 -4, R being as defined above, or any substituted or non-substituted phenyl or biphenyl,
In one embodiment the dye according to the present invention has the formula V
(formula V)
In one embodiment the dye according to the present invention has the formula VI
In one embodiment the dye according to the present invention has the formula VlI
(formula VII)
The objects of the present invention are also solved by a method of synthesis of a dye according to the present invention, comprising the following steps: a) coupling of a halogenated squarylium dye and a metalated conjugated system comprising a carboxyaldehyde moiety in its structure, as represented by scheme I
(Scheme 1)
wherein
Hal = Br, I, Cl, Tosyl
M = Sn(alkyl)3, B(OR)2, MgHaI, ZnR2, R being in this case an H or any alkyl group, preferably a C| - Ci2 alkyl, R3I-R36 and said conjugated system being as defined in any of claims 1- 7,
[Cat] representing a generally employed catalyst in such transition metal catalyzed coupling reactions, preferably palladium, nickel or copper catalyst,
and wherein 1 is a halogenated squarylium dye and 2a is metalated conjugated system comprising a carboxyaldehyde moiety in its structure
or coupling of a metalated squarylium dye and a halogenated conjugated system comprising a carboxyaldehyde moiety in its structure, as represented by the scheme II
(scheme II) wherein
Hal = Br, I, Cl, Tosyl
M = Sn(alkyl)3, B(OR)2, MgHaI, ZnR2, R being in this case an H or any alkyl group, preferably a Ci - Ci2 alkyl, R3J-R36 and said conjugated system being as defined in any of claims 1- 7,
[Cat] representing a generally employed catalyst in such transition metal catalyzed coupling reactions, preferably palladium, nickel or copper catalyst, and wherein 7 is a metalated squarylium dye and 2b is halogenated conjugated system comprising a carboxyaldehyde moiety in its structure,
and b) condensation reaction of the product of step a), with a reagent of general formula A- CH2-G, as represented by the scheme III
(Scheme III)
G, A, R31-R36 and said conjugated system being as defined above.
The objects of the present invention are also solved by a method of synthesis of a dye according to the present invention, comprising the following steps: a) coupling of a halogenated squarylium dye and a metalated conjugated system as represented by the scheme IV
3
(Scheme IV)
wherein
Hal = Br, I, Cl, Tosyl
M = Sn(alkyl)3, B(OR)2, MgHaI, ZnR2, R being in this case an H or any alkyl group, preferably a C| - Ci2 alkyl, R3 I-R36 and said conjugated system being as defined above, [Cat] representing a generally employed catalyst in such transition metal catalyzed coupling reactions, preferably palladium, nickel or copper catalyst, and wherein 1 is a halogenated squarylium dye and 2c is metalated conjugated system comprising a carboxyaldehyde moiety in its structure
or coupling of a metalated squarylium dye and a halogenated conjugated system, as represented by the scheme V
(Scheme V)
wherein
Hal = Br, I, Cl, Tosyl
M = Sn(alkyl)3, B(OR)2, MgHaI, ZnR2, R being in this case an H or any alkyl group, preferably a Ci - C)2 alkyl, R3I-R36 and said conjugated system being as defined above, [Cat] representing a generally employed catalyst in such transition metal catalyzed coupling reactions, preferably palladium, nickel or copper catalyst, and wherein 1 is a metalated squarylium dye and 2c is halogenated conjugated system
and b) introduction of a carboxyaldehyde moiety to the product of reaction a), preferably by a reaction represented by the scheme VI
POCI3 / DMF or n-BuLi / DMF
(Scheme Vl)
wherein G, A, R3I-R36 and said conjugated system being as defined above,
and c) condensation reaction of the product of step b), with a reagent of general formula A- CH2-G, as represented by the scheme VlI
A-CH2-G -H2O
wherein G, A, R3I-R36 and said conjugated system being as defined above.
The objects of the present invention are also solved by a method of synthesis of a halogenated squarylium dye X as defined above comprising the following steps:
a) formation of a halo or alkyl ester of a squaric acid derivative Ic, as represented by Scheme VlIl
(Scheme VIIl)
Hal = Br, I, Cl, Tosyl
R being any alkyl group, preferably a C| - C4 alkyl, R3 \, R33 and R34 being as defined above,
and bl) deprotection of alkyl ester to hydroxyl group, as represented by scheme IX
(Scheme IX)
followed subsequently by a condensation reaction between intermediate Id and compound Ie, as represented by Scheme X
1d ie 1
(Scheme X)
or
b2) a direct reaction between product from step a) and compound Ie, as represented by Scheme XI
1c 1e
(Scheme XI)
The objects of the present invention are also solved by an electronic device comprising a dye as defined above.
In one embodiment, said device is a solar cell, preferably a dye-sensitized solar cell. Examples of electronic devices comprising a dye in accordance with the present invention include energy supply devices for portable electronic devices and displays, such as solar cell panels for or incorporated in mobile phones, note books, laptops, portable audio-tape players, MP3- players, remote controls, e-cards, e-books, e-readers, portable CD players, portable DVD players, cameras, digicams, GPS devices, portable sensors, displays integrated in electronic devices. Examples of electronic devices in accordance with the present invention also include portable solar chargers for batteries of any of the aforementioned devices. Moreover, electronic devices in accordance with the present invention include smart windows, on-roof applications, especially in areas where a grid connection is not possible, e.g. camping cars, boats. If the electronic device in accordance with the present invention is an energy supply device, and said energy supply device is a solar cell panel, such panel is preferably a dye sensitized solar cell panel (DSSC panel) (see also figure 13).
In a preferred embodiment in the dye-sensitized solar cell, said dye is chemisorbed to a photoactive semiconductor layer.
In one embodiment the device according to the present invention, further comprises at least one other dye. Preferably, the dye in accordance with the present invention and said at least one other dye are mixed. Preferably the dye in accordance with the present invention and said at least one other dye are not on or in separate layers each, but rather being chemisorbed to one photoactive semiconductor layer.
In one embodiment said at least one other dye is red-dye or black-dye or a combination of the two.
Preferably, said dye is present in solution or said dye is present in a film.
In one embodiment the electronic device according to the present invention is a chromogenic sensor.
The objects of the present invention are also solved by the use of a dye as defined above as sensitizer in a dye-sensitized solar cell, preferably, together with at least one other dye.
In one embodiment said at least one other dye is a dye according to the present invention, as defined above, or red dye or black dye or a combination of the two.
The objects of the present invention are also solved by the use of a dye according to the present invention as a sensor, wherein, preferably, the spectral properties of said dye depend on the presence, absence or quantity of analyte present and change in accordance therewith.
In preferred embodiments, the device according the present invention comprises a semiconductor porous material, preferably with one or several of the following specifications.
- semiconductor porous material has a thickness of 10-100 nm, preferably 15-40 nm
- semiconductor porous material consist of one or more layers
- semiconductor porous material contain particles having an average diameter or length in the range of from 1 nm to 40 nm, preferably 15-30 nm
- semiconductor porous material is a mixture of more kind of particles, said one kind of particles having an average diameter or length in the range of from 1 nm to 30 nm, and said second kind of particles having an average diameter in the range of from 30 nm to 100 nm and/or length in the range of from 100 nm to 5 μm.
- semiconductor porous material can be TiO2, SnO2, ZnO, Nb2O5, ZrO2, CeO2, WO3, Cr2O3, CrO2, CrO3, SiO2, Fe2O3, CuO, Al2O3, CuAlO2, SrTiO3, SrCu2O2, ZrTiO4
- The device may possibly be a photovoltaic device containing a charge-transporting agent which can be a liquid, polymer gel based or solid state electrolyte.
- during preparation of the device, the dye molecules are adsorbed to the nanoporous particles via self-assembling out of a dye solution or a dyes-mixture solution.
The objects of the present invention are also solved by a compound represented by one of the following formulae
4
wherein R3 I-R36, R, Hal and said conjugated system are as defined in any of claims 7-8.
The term "anchoring group", as used herein, is meant to refer to any functional group that allows a covalent coupling (chemisorption) of the entity to which such anchoring group belongs, to a surface, for example the surface of a nanoporous semiconductor layer within a solar cell.
A "squarylium dye" is a molecule having one or several aromatic ring systems attached to a squaric acid derivative, which aromatic ring systems, if there are several such ring systems, may be identical or different.
A "conjugated system" is a molecule having alternating double bonds and single bonds between its atom centers. The simplest example of a conjugated system is butadiene wherein there are two double bonds separated by a single bond.
The term "molecular structure", as used herein, refers to the structure of a molecule. For example, the "molecular structure of a dye" is the structure of the molecule of said dye. An "anchoring group" that is included in the molecular structure of a dye forms part of said molecular structure.
A dye is referred to as being "chemisorbed" to a layer or surface, if the dye is covalently coupled thereto.
Term "red-dye" and "black-dye" refers to commonly used dyes for dye-sensitized solar cells which are c/5-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium(II) bis- tetrabutylammonium (in literature also known as Ruthenium 535-bisTBA, N719 or B2) and tris(isothiocyanato)-ruthenium(H)-2,2':6',2"-teφyridine-4,4',4"- tricarboxylic acid, tris- tertrabutylammonium salt (also known as Ruthenium 620-1 H3TBA, Ruthenium 620 or N- 749).
The term ' a dye including an anchoring group in its molecular structure" as used herein, is meant to refer both to a scenario where only one anchoring group is present within the structure and a scenario wherein several anchoring groups are present.
The term "covalent coupling", as used herein, is used interchangeably with the term "chemi- sorption".
In formula I, the letter "G" refers to a group which preferably is an acidic group in the sense that such group has a proton that can be dissociated from such group. Preferably, G is selected from COOH, SO3H, PO3H2, BO2H2, SH, OH, NH2. A is selected from the group comprising H, -CN, -NO2, -COOR, -COSR, -COR, -CSR, -NCS, -CF3, -CONR2, -OCF3, C6H5-mFm, wherein m = 1 -5.
The term "a molecule that is able to absorb in the wavelength range of visible and/or IR light" as used herein, is meant to refer to a molecule that is able to absorb light in only one or several parts of the entire range indicated or over the total range. For example a molecule may only absorb in the range of from 500 — 700 nm, whereas another molecule may absorb in the range of from 750 - 1000 nm, whereas a third molecule may absorb over the range of from 300 - 1200 nm. All these scenarios are meant to be encompassed by such wording.
With reference to formula II which exemplifies the "conjugated system" in accordance with the present invention, the term "a combination of the moieties are represented by formula II" is used. This is meant to encompass any molecule wherein one or several of the structures given in formula II are covalently linked to each other to also produce a "conjugated system".
A "functionalized conjugated system", as used herein, is meant to refer to a conjugated system which has been endowed with a chemical functionality that allows such conjugated system to react with other molecules. Examples for such functionalized conjugated system are a metallated conjugated system having an aldehyde group into which functionalized conjugated system an anchoring group may be introduced.
The term "substituted phenyl/biphenyl" is meant to refer to any phenyl/biphenyl wherein a hydrogen has been replaced by a substituent, such as a halogen, NO2, NH2, OH or other suitable functional groups. Such substituents have for example been defined above Ri, which substituents may also be substitutents at a phenyl or biphenyl.
The present inventors have surprisingly found dyes which by using the long wavelength region of the solar spectrum >600mm and when incorporated in DSSC show very good performance, namely >6 %, preferably >8.5 % high efficiency of DSSC, most notably compounds in accordance with formula I, such as compound 5 and 27.
The present inventors have moreover surprisingly found that if one endows organic dyes having molecular structure represented by formula I, these dyes are very well suited to be used in dye sensitized solar cells and sensor devices. The inventors have devised methods of synthesis for producing such dyes, and these dyes effectively adsorb on nanoporous semiconductor layers, such as TiO2, they are active sensitizers in the visible, but also in the red/IR region of the solar spectrum which is a region where the standard Ruthenium based dyes, red- and black- dye, and other organic dyes, as 21 and 22, are not active. Moreover, the dyes according to the present invention show high quantum efficiency similar to that of the standard red-dye, but at in the longer wavelength region of the solar spectrum. If one therefore combines the dyes of the present invention with other dyes, such as other organic dyes or standard red dye or standard black dye, a broad range of the solar spectrum may be harvested. That makes the dyes of the present invention very promising to be used together with other dyes, such as organic dyes, standard red dye or standard black dye or further dyes according to the present invention with absorption maxima at different wavelengths. A dye sensitized solar cell comprising a dye according to the present invention, and, in addition thereto, one or more further dyes, is herein also referred to as a multiple-dyes sensitized solar cell (M-DSSC). Preferably, said one or more further dyes is also a dye according to the present invention.
Further, organic dyes have high absorption coefficients. This means it needs less amount of dye to absorb the same amount of light. Less amount of one dye on a surface enables the use of more dyes with different absorption properties, ideally being a mixture of dyes absorbing the whole range of the sun spectrum.
Moreover, in the dyes according to the present invention, the anchoring group consists of a group represented by the general formula
A G which is directly or optionally bridged by a conjugated system to the main core of the dye. Without wishing to be bound by any theory, the present inventors believe that this kind of anchoring group influences the electron density distribution in such way that after photo-
excitation a fast electron injection occurs. The dye is directly attached to the semiconductor surface, such as the TiO2 surface via the group G of the anchoring group. At the same time, the A-group of the anchoring group shown above, having an electron acceptor character is believed to have a positive effect on electron injection from the dye to the semiconductor. Again, without wishing to be restricted to any specific mechanisms, the present inventors believe, and molecular orbital calculations support their assumption that in the ground state, the electron density is localized on the chromophore or dye moiety, far away from the semiconductor surface. After photo-excitation, effective charge separation and electron fast migration from the dye-moiety next to the anchoring group via the conjugated system if present, otherwise directly, takes place. This process is promoted by the acceptor character of the A-group of the anchoring group. The electron distribution changes in such a way that the electron density becomes highest in the proximity of anchor group. The electron transfer from here to the conduction band of the semiconductor is therefore fast. This hypothesized intramolecular electron density relocation induced by photo-excitation is similar to the intra-molecular metal- ligand-charge-transfer in standard red dye.
The energy levels (HOMO/LUMO) of an organic dye can systematically be tuned by chemical structure modification in such a manner that they match with the other components of the DSSC: The energy level of the excited state of the dye (LUMO) with the conduction band of the semiconductor and the ground state energy level of the dye (HOMO) with the redox potential of the redox pair. If a conjugated system is present, its role is to allow the fast electron flow through the system and thus, the distribution relocation after photo-excitation. Further, an extended π-conjugation results in an additional red-shift of the absorption.
In the following, reference is made to the figures, wherein, figure 1 shows an example of a synthesis scheme of one embodiment of a dye according to the present invention, wherein a halogenated chromophore is reacted with a metalated conjugated system comprising a carboxyaldehyde moiety in its structure, and thereafter the car- boxyaldehyde moiety is transformed into an anchoring group,
figure 2 shows an example of a synthesis scheme of one embodiment of a dye according to the present invention, wherein a metalated chromophore is reacted with a halogenated conjugated system comprising a carboxyaldehyde moiety in its structure, and thereafter the carboxyaldehyde moiety is transformed into an anchoring group,
figure 3 shows an example of a synthesis scheme of one embodiment of a dye according to the present invention, wherein first a metalated conjugated system is reacted with a halo- genated chromophore, and thereafter the carboxyaldehyde moiety is introduced, which thereafter is transformed into an anchoring group,
figure 4 shows an example of a synthesis scheme of one embodiment according to the present invention, wherein first a halogenated conjugated system is reacted with a metalated chromophore, and thereafter the carboxyaldehyde moiety is introduced, which thereafter is transformed into an anchoring group,
figure 5 shows an example of a synthesis scheme of one embodiment according to the present invention, wherein an intermediate, the halogenated squarylium dye of general formula 1 is produced,
figure 6 shows a synthesis scheme of a dye in accordance with the present invention having a cyano acrylic acid moiety as anchoring group directly attached to the chromophore , which is squarylium dye, being represented by general formula I with n2 = 0,
figure 7 shows an example of a synthesis scheme of one embodiment according to the present invention, wherein a sensitizer dye 27 is produced,
figure 8 shows the structure of different sensitizer dyes prepared according to the present invention,
figure 9 shows the structure of different dyes which were investigated for comparison as sensitizer in DSSC and used in mixture with sensitizer dyes according to the present invention in M-DSSC: 21, 22 = organic dyes from the class of the merocyanine dyes; 23 = standard black dye and 24 = standard red dye which are the conventional sensitizers used in DSSC; 14 and 17 = sensitizer dye from the similar class of squarylium dyes, but having different molecular structure as given by general formula 1 (without specific anchoring group)
figures 10 shows the electron distribution of dye 5 in accordance with the present invention in the ground and excited state; molecular modeling was performed, calculations are based on density functional theory using materials studio software from Accelrys,
figure 1 1 shows the electron distribution of dye 26 in accordance with the present invention in the ground and excited state; molecular modeling was performed, calculations are based on density functional theory using materials studio software from Accelrys,
figure 12 shows the energy levels of different sensitizer dyes according to present invention obtained by theoretical calculations; calculations (molecules in vacuum) are based on density functional theory using materials studio software from Accelrys,
figure 13 shows various embodiments of electronic devices in accordance with the present invention which include energy supply devices, such as DSSC panels, in accordance with the present invention.
Moreover reference is made to the following examples which are given to illustrate, not to limit the present invention.
Examples
Hereinafter, examples for the synthesis of the dyes and their intermediates, characterization and application of the dyes as sensitizers in DSSC will be described.
Example 1: Synthesis of sensitizer dye 5 with general formula V being described in claims 1- 5 and having a cyano acrylic acid moiety attached to a squarylium dye as anchoring group via a thiophene as conjugated system by two different synthetic routes described above.
1) This is an example of the general synthesis scheme depicted in figure 1.
2 is metalated conjugated system comprising a carboxyaldehyde in its structure step a) Reaction of 1 and 2 by palladium mediated coupling reaction resulting in formation of compound 4; step b) transformation of carboxyaldehyde moiety into anchoring group by reaction of 4 with cyano acetic acid to the targeted 5.
Step a) Under inert atmosphere, to a mixture of chromophore 1 in toluene/methanol mixture, 1 mol % catalysator Pd(PPh3).!, 1 -2 equivalent of thiophene-carbaldehyde boronic acid were added. The reaction mixture was stirred at 120°C for 12 h. After cooling to room temperature, the solvent was removed under reduced pressure. The mixture was extracted with dichloro- methane and the solvent removed under reduced pressure. Purification of the crude product was performed by column chromatography on silica gel with (6/4) dichloromethane/ acetone to give the pure thiophene-carbaldehyde derived 4.
Step b) A mixture of compound 4 and cyano acrylic acid in acetonitrile are heated in the presence of small amount of piperidine to 80°C for 12 hours. After cooling, the solvent is removed under reduced pressure and the crude product is purified by column chromatography on silica gel with (5/5) acetone/ ethylacetate to give the dye 5 as a green red shining powder.
2) This is an example of the general synthesis scheme depicted in figure 3
1 is halogenated chromophore
2 is metalated conjugated system
step a) Reaction of 1 and 2 by palladium mediated coupling reaction results in formation of compound 3; step b) The carboxylaldehyde moiety is introduced to compound 3 by ViIs- maier-Haak reaction; And step c) carboxyaldehyde moiety is transformed to anchoring group by reaction of 4 with cyano-acetic acid resulting in targeted 5.
Step a) Under inert atmosphere, to a mixture of chromophore 1, 1 mol % catalysator Pd(PPh3 )4, 1 equivalent of CsF in toluene, 1.2 equivalent of tributylstannyl-thiophene were added. The reaction mixture was stirred at 1200C for 12 h. After cooling to room temperature, dichloromethane was added. The white salt (Bu3SnF) formed during the reaction was filtered off and the solvent removed under reduced pressure. Purification of the crude product was performed by column chromatography on silica gel with (4/6) dichloromethane/ ethylacetate to give the pure thiophene derived squarylium dye 3.
Step b) Under inert atmosphere, compound 3 is dissolved in anhydrous DMF. 1 equivalent of POCl3 is slowly added and the mixture stirred at 700C for 4 hours. The mixture was allowed to cool down to room temperature, ice and water and aqueous NaOH for neutralisation were added. The mixture is extracted with dichloromethane and the solvent removed under reduced pressure. The crude product was purified by column chromatography on silica gel with (2/8) acetone/ ethylacetate to give the pure compound 4.
Step c) A mixture of compound 4 and acrylic acid in acetonitrile were heated in the presence of small amount of piperidine to 800C for 12 hours. After cooling, the solvent was removed under reduced pressure and the crude product was purified by column chromatography on silica gel with (5/5) acetone/ ethylacetate to give the dye 5 as a green red shining powder.
Example 2: Synthesis of a halogenated squarylium dye X by the route described above and depicted in figure 5
Step a) formation of alkyl ester of a squaric acid derivative Ic
Step b) first deprotection of alkyl ester group to result in Id followed by reaction with Ie to give the brominated squarylium dye 1.
Semisquaric acid derivative Ic was poured in ethanol and a few drops of 0.5 M aq. NaOH were added. The mixture was stirred for 3h at 700C. After cooling IM HCl were added. By evaporation of solvent product Id is isolated as yellow solid. Id was than further reacted with 1 equivalent of Ie in a 1 :1 mixture of 1 -butanol/toluene in the presence of pyridine. Under reflux (130°C), the reaction generated water that was removed by azeotropic distillation or by using molecular sieves. After 1 h reaction time, formation of squarylium dye was indicated by the appearance of a blue-green colour. After 12 h at 130 0C, the reaction mixture was allowed to cool to room temperature and the solvent removed under reduced pressure. The crude product was purified by column chromatography on silica gel with (8/2) dichloro- methane/ethylacetate as eluent . The pure product 1 was isolated as green solid.
Example 3: Analytical data of dyes and intermediates described above
Analytical data for compound 1
C35H39BrN2O2 (599.60)
IH NMR (400MHz, CDCl3): δ= 7.35-7.20 (m, 4H, arH), 7.09 (t, IH, arH), 6.95 (d, IH, arH),
6.74 (d, IH, arH), 5.92 (s, IH, =CH-), 5.84 (s, IH, =CH-), 4.05, 3.83 (brs, 4H, N-CH2), 1.96-
1.70 (m, 16H, CH2-Propyl, CH2-Hex, 6H, CH3), 1.21 (t, 6H, CH3-Et), 1.26-1.23 (brs, 12H,
CH2), 0.95 (t, 3H, CH3-Hex or CH3-Propyl), 0.80 (t, 3H, CH3-Hex or CH3-Propyl)
ESI MS m/z = 601.3 [M+].
UV/VIS (acetonitrile): λmax = 636 nm.
Analytical data for compound 3
C39H44N2O2S (604.84)
IH NMR (400MHz, MeOD): δ= 7.71 (s, I H, arH), 7.62 (d, I H, arH), 7.43 (d, I H, arH), 7.39-
7.34 (m, 3H, arH), 7.25-7.18 (m, 3H, arH), 7.08 (t, IH, arH), 5.83 (d, IH, H-7), 5.98 (s, I H,
=CH-), 5.94 (s, IH, =CH-), 4.09 (q, 4H, N-CH2), 1.81-1.23 (m, 8H, CH2-Hex), 1.74 (s, 6H,
CH3), 1.21 (t, 6H, CH3-Et), 1.24 1.72 (brs, 12H, CH3), 1.06 (t, 6H, CH3-Hex or CH3-
Propyl), 0.91 (t, 6H, CH3-Hex or CH3-Propyl)
ESl MS nVz = 605.3 [M+].
UV/VIS (acetonitrile): λmax = 645 nm.
Analytical data for 4
C40H44N2O3S (632.85)
IH NMR (400MHz, CDC13): δ= 9.89 (s, IH, H-aldehyde), 7.76 (d, IH, arH), 7.64 (m, 2H, arH), 7.42-7.32 (m, 4H, arH), 7.19 (t, IH, arH), 7.05 (d, IH, arH), 6.97 (s, IH, arH), 5.98 (s,
IH, =CH-), 5.34 (s, IH, =CH-), 4.02 (brs, 2H, N-CH2), 3.95 (brs, 2H, N-CH2), 1.81 -1.23 (m,
8H, CH2-Hex), 1.74 (s, 6H, CH3), 1.21 (t, 6H, CH3-Et), 1.24 1.72 (brs, 12H, CH3), 1.06 (t,
6H, CH3-Hex or CH3-Propyl), 0.91 (t, 6H, CH3-Hex or CH3-Propyl)
ESI MS m/z = 633.4 [M+].
UWVIS (acetonitrile): λmax = 654 nm.
Analytical data for 5
C43H45N3O4S (699.31)
IH NMR (400MHz, CDC13): 6= 8.18 (s, IH, =CH-), 7.79 (d, IH, arH), 7.31 (d, IH, arH),
7.42-7.32 (m, 4H, arH), 7.19 (dd, I H, arH), 7.01 (d, IH, arH), 6.95 (s, IH, arH), 5.98 (s, IH,
=CH-), 5.34 (s, IH, =CH-), 4.02 (brs, 2H, N-CH2), 3.95 (brs, 2H, N-CH2), 1.81-1.23 (m, 8H,
CH2-Hex), 1.74 (s, 6H, CH3), 1.21 (t, 6H, CH3-Et), 1.24 1.72 (brs, 12H, CH3), 1.06 (t, 6H,
CH3-Hex or CH3-Propyl), 0.91 (t, 6H, CH3-Hex or CH3-Propyl)
ESI MS m/z = 700.3 [M+].
UV/VIS (acetonitrile): λmax = 665 nm.
Example 4: Molecular modelling - theoretical calculations of dye 5 having a cyano acrylic acid moiety attached as anchoring group to squarylium dye as chromophore via a thiophene as conjugated system an
Molecular modeling was performed by using Materials Studio 4.0 DMoB software based on density functional theory. This dye exhibits physical properties described below. The high
performance of the dye as sensitizer in DSSC is attributed to the structure of the dye according to this invention and represented by general formula I.
Figure 12 shows energy levels of different dyes according to present invention including for comparison the energy levels of other components of the DSSC, redox pair and semiconductor conduction band. The structure of the dyes is given in figure 8. The sensitizer dyes absorb light in the range > 630 nm and the efficiency of the DSSC prepared with these sensitizers shows efficiencies > 6%. The energy levels of the dyes are well matched to semiconductor and redox-pair. These properties are strongly related with the nature of the chromophore and conjugated system.
Figure 10 shows the electron distribution in ground and excited state of the sensitizer dye 5 and figure 11 of the sensitizer 26. For both, the nature of the anchor group allows an intramolecular relocation of the electron density by photoexcitation. Respectively, on the left side of the figure the molecule in ground state shows the electron density is highest on the chromophor, far away from the semiconductor surface. On the right side the LUMO of the molecule is depicted. This is correlated with the electron distribution of the molecule after photoexcitation. After photoexcitation, the electron density is very high in the vicinity of the anchoring group that allows the direct coupling with the nanoporous semiconductor. The present inventors believe that this situation enables a very fast electron injection.
Hence, overall, in the present application, dyes are disclosed which are stable and are characterized by a strong absorption and emission in the visible and IR region of the solar spectrum, and they are useful as sensitizers in DSSCs for these regions. In combination with the standard red-dye, or standard black -dye or other organic dyes, they are able to collect the solar light over a broad range of the solar spectrum. The present inventors describe a molecular design of these dyes for improved performance in dye-sensitized solar cells. The anchoring group is believed to be responsible for the efficient adsorption of the dye-sensitizer onto the nanoporous semiconductor surface and consist of an acrylic acid moiety which is optionally bridged by a conjugated system to the main core of the dye. This kind of anchoring group is believed to enable a photo-excitation induced intramolecular electron density relocation in organic dyes resulting in better performance of the sensitizer in a photovoltaic device.
Example 5: UV-Vis of an ethanol solution of sensitizer dye 5 and for comparison standard black dye 23 and standard red dye 24.
Wavelenght [nm]
The absorption of compound 5 is strongly red shifted with maximum at 664 nm. Compared to the Ruthenium based dyes 23 and 24 which are the conventional sensitizers used in DSSC, dye 5 has a strong absorption with extinction coefficient being almost 15 times higher.
Example 6: General protocol for preparing solar cells by using a) a 10-20 μm-thick mono-printed porous layer of TiO2 semiconductor particles of 0.24 cm2 active area b) a 20-30 μm-thick multi-printed porous layer of TiO2 semiconductor particles of 0.1882 cm2 active area
The DSSCs are assembled as follows: A 30-nm-thick bulk TiO2 blocking layer is formed on FTO (approx. 100 nm on glass or flexible substrate). A 10-30 μm-thick porous layer of semiconductor particles is screen printed on the blocking layer and sintered at 450 °C for half an hour. Dye molecules are adsorbed to the nanoporos particles via self-assembling out of a dye- solution. The dye-solution consists of a single dye or single dye and an additive, such as de- oxycholic acid or a mixture of dye in different ratio or a mixture of dye in different ratio and an additive. The porous layer is filled with a) liquid electrolyte b) polymer gel electrolyte containing IVI3 " as redox couple (15 mM) by drop casting. A reflective platinum back electrode is attached with a distance of 6 μm from the porous layer.
Example 7: Measuring the efficiency of DSSCs containing at least one of the sensitizer dye produced by the method of the present invention. The respective structure of the dyes is given in Figure 8 and 9.
The quality of the cells is evaluated by means of current density (J) and voltage (V) characteristics under illumination with light from a) a sulphur lamp (IKL Celsius, Light Drive 1000) with an intensity of 100 mW cm"2. If not otherwise stated, the results are averages over three cells. b) a sun simulator (AMI .5G YSS-150) with an intensity of 100 mW cm'2. If not otherwise stated, the results are averages over three cells.
The efficiency of a photovoltaic device is calculated as follows: η = Pou, / Pin = FF x (Jscx Voc) / (L x A)
FF = fill factor
Voc = open circuit voltage
J sc = short current density
L = intensity of illumination = 100 mW/ατr
A = active area = 0.24 cm2
Vmax = voltage at maximum power point
Jmax = current at maximum power point
An important parameter for judging the performance of a dye as sensitizer in DSSC is the IPCE curve. The IPCE curve reflects the photo-activity of the sensitizer dyes at different wavelengths (IPCE = incident photon to current efficiency).
For having a better comparison by measuring the efficiency of DSSCs containing the sensitizer dyes of the present invention in most cases, as reference, a cell containing the commercial standard red dye (so called bisTBA-Ru535 or N719) or black dye (so called Ru620- 1H3TBA or N749) is prepared under same conditions.
Example 8: Comparing efficiency of the DSSC by using squarylium dye 5, 14 and 17, respectively
DSSCs were prepared by method described in Example 6a and measured by method described in 7a.
The three dyes belong to the same class of dyes, namely squarylium dyes. Dye 5 and 14 have thiophene moieties attached to the squarylium dye core, which shifts the absorption in the more red region of solar spectrum. Dye 5 and 17, both have only one anchor group, but sensitizer dye 5 has the molecular structure and specially the anchoring group according to any of claims 1-5.
[1] TiO2 dye-coating from 0.125 mM dye solution + with additive deoxycholic acid 20 mM. [2] TiO2 dye-coating from 0.3 mM dye solution + with additive deoxycholic acid 20 mM.
The efficiency of the DSSC prepared with sensitizer dye 5 shows much higher efficiency (>6%) as the ones prepared with the other two dyes. This is the highest efficiency of a DSSC ever reported for a device prepared by using an organic dye absorbing light in long wavelength range of solar spectrum > 600 nm.
The superiority of the sensitizer dyes with a structure according to any of claims 1-5, such as 5 or 27, over other organic dyes is reflected by the fact that this sensitizer dye can be used in mixture with other sensitizer dye resulting in higher efficiency of the solar cell than using a single sensitizer dye. The inventors name this type of solar cell device in which more than one dye is used as sensitizer for harvesting the light Multiple-dyes sensitized solar cell (M- DSSC).
Example 9: Efficiency of M-DSSC containing sensitizer dye 5 and the standard black dye 23 prepared by the method described in Example 6a and measured according to Example 7a. For comparison also DSSCs prepared with the respective single sensitizer dye were prepared and measured.
[1] TiO2 dye-coating from 0.125 mM dye solution + with additive deoxycholic acid 12.5 mM. [2] TiO2 dye-coating from 0.375 mM dye solution + with additive deoxycholic acid 20 mM. [3] TiO2 dye-coating from a dyes mixture solution (dye 5 0.125 mM, + dye 23 0.375 mM + with additive deoxycholic acid 20 mM).
By using a solution in which the dyes are mixed in ration 1 :3 the efficiency DSSC is increased. This is mostly due to the increased short current density.
Usually, in the field of DSSC standard black dye 23 is preferably used instead standard red dye 24 when high photo-activity in the long wavelength region of solar spectrum is needed. By comparing the IPCE curves of 5 and standard black dye 23, it can be seen that dye 5 having structure according claim 1 shows much higher photo-activity in the range of 550-750 nm than black dye 23.
Further, in the IPCE curves it can be seen that the incident-photon-conversion-efficiencies of the two dyes 5 and 23 behave in an additive way; therefore the dye mixture has better performance than the single dyes. This is the first time that such a phenomenon is realized.
IPCE-curves
300 400 500 600 700 800 900 Wavelenght [nm]
Example 10: Efficiency of M-DSSC containing sensitizer dye 5 and the organic dye 21 prepared by the method described in Example 6a and measured according to Example 7a. For comparison also DSSCs prepared with the respective single sensitizer dye were prepared and measured.
[1] TiO2 dye-coating from 0.125 mM dye solution + with additive deoxycholic acid 12.5 mM. [2] TiO2 dye-coating from 0.125 mM dye solution + with additive deoxycholic acid 12.5 mM. [3] TiO2 dye-coating from a dyes mixture solution (dye 5 0.125 mM, + dye 21 0.125 mM + with additive deoxycholic acid 20 mM)
Both dyes show high efficiencies. By using a solution in which the dyes are mixed in 1 :1 ratio the efficiency of the DSSC devise increases. This is mostly due to the increased short current density.
By comparing the IPCE curves of 5 and dye 21, it can be seen that dye 5 is photo-active in the range of 550-750 nm where standard dyes 23 and 24 and also organic dye 21 doesn't have so high or any photo-activity in this region.
The IPCE curve of the dye mixture is a mirror of the added IPCE curve of the single dyes.
This is the reason why the dye mixture performs better than the single dyes.
This is the first time reported that such a mixture of pure organic dyes lead to higher efficiency in DSSC.
IPCE-curves
mixture
Wavelenght [nm]
Example 11: Efficiency of M-DSSC containing sensitizer dye 5 and the organic dye 22 prepared by the method described in Example 6a and measured according to Example 7a.. For comparison also DSSCs prepared with the respective single sensitizer dye were prepared and measured.
[1] TiO2 dye-coating from 0.125 mM dye solution + with additive deoxycholic acid 12.5 mM. [2] TiO2 dye-coating from 0.125 mM dye solution + with additive deoxycholic acid 12.5 mM. [3] TiO2 dye-coating from a dyes mixture solution (dye 5 0.125 mM, + dye 22 0.125 mM + with additive deoxycholic acid 20 mM).
Both dyes show high efficiencies. By using a solution in which the dyes are mixed in 1 :1 ratio the efficiency of the DSSC devise increases. This is due to the additive behavior of the individual short current density.
By comparing the IPCE curves of 5 and dye 22, it can be seen that dye 5 is photo-active in the range of 550-750 nm where standard dyes 23 and 24 do not have as high photo-activity and organic dye 22 does not have any photo-activity.
IPCE-curves
Example 12: Efficiency of M-DSSC prepared by method described in Example 6a and measured according to Example 7a by using a mixture of three sensitizers: sensitizer dye 5, standard black dye 23 and organic dye 21. For comparison also DSSCs prepared with the respective single sensitizer dye were prepared and measured.
[1] Tiθ2 dye-coating from 0 125 mM dye solution + with additive deoxychohc acid 12 5 mM
[2] TiO2 dye-coating from 0 125 mM dye solution + with additive deoxychohc acid 12 5 mM
[3] TiO2 dye-coating from a dyes mixture solution (dye 5 0 125 mM. + dye 22 0 125 mM + dye 23 0 375 mM with additive deoxycholic acid 20 mM).
The three dyes have similar efficiency as single sensitizer. By mixing the dyes higher efficiency of DSSC is achieved. By using a solution in which the dyes are mixed in 1 :1 :1 ratio the efficiency of the DSSC devise increases. The dyes are photo-active in different regions of solar spectrum. The IPCE curve of the mixture is extended to the red region due to effect of black dye, and is more intense in the range of 580-780 nm due to dye 5.
IPCE-curves
dyes mixture
300 400 500 600 700 800 900 Wavelenght [nm]
This is the first time that a DSSC with increased efficiency due to employing a mixture of three dyes is reported.
Usually, when two or more dyes are mixed the gain that is achieved by addition of the harvested light by second dye is lost due to a decrease of the performance of the first dye. To show this, three examples that the inventors investigated are disclosed in the following.
In a previous patent application of MSL-Sony WO2005/024866 -Tandem cell the inventors disclose the possibility to avoid the loss mentioned above when using two dyes. [6] In order to have an increase of DSSC efficiency, the device of WO 2005/024866 needs to be built in the "Tandem geometry". In this case the dyes are not mixed, they are coated on two nanoporous layers and used in the device in two separate compartments. For actual mass production, this is a device assembly which is not really economically practicable, because, for mass production, it is a too complicated and costly procedure.
Example 13: Efficiency of M-DSSC containing the organic sensitizer dye 24 and 14 prepared by the method described in Example 6b and measured according to 7a. For comparison also DSSCs with the respective single sensitizer dye were prepared and measured. The dye- solution concentration employed for nanoporous TiO2 coating are the in previous determined optimum concentrations.
[1] TiC>2 dye-coating from 0.125 mM dye solution + with additive deoxycholic acid 20 mM. [2] Tiθ2 dye-coating from 0.3mM dye solution + no additive.
[3] T1O2 dye-coating from a dyes mixture solution (dye 14 0.125 mM, + dye 24 0.3 mM + no additive).
It can be clearly seen from the data that by mixing the dyes no higher efficiency of the DSSC device is achieved. This is mainly due to decreased in short current density of the standard sensitizer dye 24 by addition of 14.
This is confirmed by recording the IPCE curves. In this case, the red dye 24 alone has a much higher photo-activity when used as single dye than mixed with sensitizer dye 14. There is no additive behavior.
-m - 24
Wavelenght [nm ]
Example 14: Efficiency of M-DSSC containing the organic sensitizer dye 24 and 17 prepared by the method described in Example 6a and measured according to Example 7b. For comparison also DSSCs with the respective single sensitizer dye were prepared and measured. The dye-solution concentration employed for nanoporous TiO2 coating are the in previous determined optimum concentrations.
[I] TiC>2 dye-coating from 0.3 mM dye solution + with additive deoxycholic acid 20 mM.
[2] TiC>2 dye-coating from 0.3mM dye solution + no additive.
[3] TiC>2 dye-coating from a dyes mixture solution (dye 17 0.3 mM, + dye 24 0.3 mM + no additive).
By adding dye 17 to standard red dye 24 a decrease in efficiency and IPCE curve is clearly to see.
IPCE curve
Wavelenght [nm]
Example 15: Efficiency of DSSC by using sensitizer dye 5 and 27 prepared by the method described in Example 6b and measured according to Example 7a.
[1] T1O2 dye-coating from 0.125 mM dye solution + with additive deoxycholic acid 12.5 mM.
Example 16: Efficiency of M-DSSC containing the organic sensitizer dye 24 and 5 prepared by the method described in Example 6b and measured according to Example 7b. For comparison also DSSCs with the respective single sensitizer dye were prepared and measured.
[1] TiO? dye-coating from 0.125 mM dye solution + with additive deoxycholic acid 12.5 mM.
[2] TiC>2 dye-coating from 0.3mM dye solution + no additive.
[3] Tiθ2 dye-coating from a dyes mixture solution (dye 5 0.125 mM, + dye 24 0.3 mM + 10 mM DCA).
This is the first time that the efficiency of a DSSC increases by using a mixture of standard red dye and an organic dye.
Example 17: Efficiency of DSSCs prepared by the method described in Example 6b and measured according to Example 7b with sensitizer dye 5 and as comparison with other organic sensitizer dye 21 and 22.
[1] TiO2 dye-coating from 0.125 mM dye solution + with additive deoxycholic acid 12.5 mM.
The dyes 21 and 22 have a similar anchoring group, but they do not have any activity in the long wavelength region of solar spectrum as dye 5.
The efficiency of the DSSC prepared with sensitizer dye 5 has much higher efficiency as the other organic dyes 21 and 22.
6.09 % is the highest efficiency ever reported of a DSSC measured under sun simulator illumination and by using an organic dye absorbing light in long wavelength range of solar spectrum > 600 nm. All other organic dyes showing good performance in DSSC such as 21 or 22 absorb light in the range of 300-550 nm.
Example 18: Efficiency of DSSCs prepared by the method described in Example 6b and measured according to Example 7b by using individual or mixture of dye 5, 21, 22 and 23. For comparison also DSSCs prepared with the respective single sensitizer dye were prepared and measured.
[1] TiO2 dye-coating from 0.125 mM dye solution + with additive deoxycholic acid 12.5 mM.
[2] TiO2 dye-coating from a dyes mixture solution (dye 5 0.125 mM, + dye 21 0.125 mM or dye 23 0.125 mM + additive deoxycholic acid 20 mM).
[3] TiO2 dye-coating from a dyes mixture solution (dye 50.125 mM, + dye 21 0.125 mM + dye 230.375 mM + additive deoxycholic acid 20 mM).
By using a solution in which the dyes are mixed the efficiency DSSC is increased. This is mostly due to the increased short current density.
Example 19
Synthesis scheme of dye 26 being described in claim 1-5 with trifluoromethyl acrylic acid moiety as anchoring group attached to squarylium dye as a chromophore via a thiophene as conjugated system.
This is an example of the general synthesis scheme depicted in figure 1.
26
1 is halogenated chromophore
2a is metalated conjugated system comprising a carboxyaldehyde in its structure step a) Reaction of 1 and 2a by palladium mediated coupling reaction resulting in formation of compound 4; step b) transformation by reaction of 4 with triflυoropropionic acid to the targeted 26.
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Y. Ohga, A. Shinpou, Y. Abe, S. Suga, H. Arakawa, J. Phys. Chem B, 2002, 106, 1363; c) K. Hara, T.
Kinoshita, K. Sayama, H. Sugϋiara, H. Arakawa, Sol. Energy Mater. Sol. Cells. 2000, 64, 1 15. [4] a) K. G. Thomas, P. V. Kamat, Ace Chem. Res. 2003, 36, 888; b) K.Y. Law, Chem. Rev. 1993, 93, 449-486; c) Kim, Sung-Hoon; Han, Sun-Kyung, High performance squarylium dyes or high-tech use.. Coloration Technology (2001), 1 17(2), 61-67. d) Chu, et al. Benzpyrylium squarylium and croconylium dyes, and processes for their preparation and use, US1999/065350; e) Satsuki, Makoto; Oga, Yasuyo; Shinpo, Akira; Suga, Sadaharu, Squarylium indole cyanine dyes with good solubility in organic solvents, preparation thereof, and light absorbers therefrom, JP 2002/294094; f) Lin, Tong; Peng, Bi-Xian, Synthesis and spectral characteristics of some highly soluble squarylium cyanine dyes, Dyes and Pigments 1997, 35(4), 331 -338.
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Claims
A dye represented by formula I
(formula 1)
G being an anchoring group, said anchoring group allowing a covalent coupling of said dye to a surface, for example a surface of a nanoporous semiconductor layer, said anchoring group being selected from -COOH, -SO3H, -PO3H2, -BO2H2, -SH, -OH, -NH2, preferably -COOH,
wherein A is selected from the group comprising H, -CN, -NO2, -COOR, -COSR, -COR, - CSR, -NCS, -CF3, -CONR2 -OCF3, C6H5-1JFn,, wherein m = 1 - 5, preferably -CN or -CF3, R being H or any straight or branched alkyl chain of general formula -CnH2n+I, n = 0-12, preferably 0-4,
wherein R31, R32, R33, R34, R35, R36 , at each occurrence, are independently selected from H or any straight or branched chain of general formula -(CH2)nCH3, -(CH2)n-COOR, -(CH2)n-OR, -
(CH2)n-SR, -(CH2VNR2, -((CH2)p-O)n-CH3, n = O - 12, preferably 0-6, and p= 1 -4, R being as defined above, or any substituted or non-substituted phenyl or biphenyl,
wherein said conjugated system is represented by a moiety shown in formula II
or a combination of any of the moieties represented by formula 11,
wherein ni and n2 = 0 - 12, preferably ni = 0-3 and n2 = 1-7, wherein R3 is selected from
H, -(CH2)nCH3, -(CH2)n-COOR, -(CH2)n-OR, -(CH2)n-SR,
-(CH2VNR2, -((CH2)P-O)n-CH3, p= 1-4, n = 0-12, R being as defined above, and wherein R| is selected from halogen, such as Cl, Br, F, I, or NO2, NH2, CN, SO3H, OH, H, -(CH2)nCH3, -(CH2)n-COOR,
-(CH2)n-OR, -(CH2)n-SR, -(CH2VNR2, -((CH2)P-O)n-CH3, p= 1-4, n = 0-12,
R being as defined above.
2. The dye according to claim 1 , being able to absorb in the wavelength range of visible and/or IR light, preferably in the range from 300-1200 nm, or a subrange thereof, preferably 580-850 nm,
3. The dye according to any of claims 1-2, having the formula III
(formula III)
4. The dye according to any of the foregoing claims, having the formula IV
(formula IV)
5. The dye according to any of claims 1-3, having the formula V 
(formula V)
or formula VI
(formula VI)
or formula VII
(formula VII)
6. A method of synthesis of a dye according to any of claims 1-5, comprising the following steps: a) coupling of a halogenated squarylium dye and a metalated conjugated system comprising a carboxyaldehyde moiety in its structure, as represented by the scheme I 
(Scheme 1) wherein
Hal = Br, I, Cl, Tosyl
M = Sn(alkyl)3, B(OR)2, MgHaI, ZnR2, R being in this case an H or any alkyl group, preferably a Cj - Ci2 alkyl, R3J-R36 and said conjugated system being as defined in any of claims 1-5,
[Cat] representing a generally employed catalyst in such transition metal catalyzed coupling reactions, preferably palladium, nickel or copper catalyst, and wherein 1 is a halogenated squarylium dye and 2a is metalated conjugated system comprising a carboxyaldehyde moiety in its structure
or coupling of a metalated squarylium dye and a halogenated conjugated system comprising a carboxyaldehyde moiety in its structure, as represented by the scheme II
Hal = Br, I, Cl, Tosyl
M = Sn(alkyl)3, B(OR)2, MgHaI, ZnR2, R being in this case an H or any alkyl group, preferably a C| - Ci2 alkyl, R31-R36 and said conjugated system being as defined in any of claims 1-5,
[Cat] representing a generally employed catalyst in such transition metal catalyzed coupling reactions, preferably palladium, nickel or copper catalyst, and wherein 7 is a metalated squarylium dye and 2b is halogenated conjugated system comprising a carboxyaldehyde moiety in its structure,
and b) condensation reaction of the product of step a), with a reagent of general formula A- CH2-G, as represented by the scheme Hl
A-CH2-G -H2O
5
(Scheme III)
G, A, R3I-R36 and said conjugated system being as defined in any of claims 1-5,
7. A method of synthesis of a dye according to any of claims 1-5, comprising the following steps: a) coupling of a halogenated squarylium dye and a metalated conjugated system as represented by the scheme IV 
(Scheme IV)
wherein
Hal = Br, I, Cl, Tosyl
M = Sn(alkyl)3, B(OR)2, MgHaI, ZnR2, R being in this case an H or any alkyl group, preferably a Ci — Ci2 alkyl, R3J-R36 and said conjugated system being as defined in any of claims 1-5,
[Cat] representing a generally employed catalyst in such transition metal catalyzed coupling reactions, preferably palladium, nickel or copper catalyst, and wherein 1 is a halogenated squarylium dye and 2c is metalated conjugated system comprising a carboxyaldehyde moiety in its structure
or coupling of a metalated squarylium dye and a halogenated conjugated system, as represented by the scheme V
+ Hal — -conjugated system 
7
[Cat]
3
(Scheme V)
wherein
Hal = Br, I, Cl, Tosyl
M = Sn(alkyl)3, B(OR)2, MgHaI, ZnR2, R being in this case an H or any alkyl group, preferably a Cj - Cj2 alkyl, R31 -R36 and said conjugated system being as defined in any of claims 1-7,
[Cat] representing a generally employed catalyst in such transition metal catalyzed coupling reactions, preferably palladium, nickel or copper catalyst, and wherein 1 is a metalated squarylium dye and 2c is halogenated conjugated system
and b) introduction of a carboxyaldehyde moiety to the product of reaction a), preferably by a reaction represented by the scheme Vl
POCI3 / DMF or n-BuLi / DMF
(Scheme VI) wherein G, A, R31-R36 and said conjugated system being as defined in any of claims 1-5.
and c) condensation reaction of the product of step b), with a reagent of general formula A- CH2-G, as represented by the scheme VlI
A-CH2-G -H2O
wherein G, A, R3J-R36 and said conjugated system being as defined in any of claims 1-5.
8. A method of synthesis of a halogenated squarylium dye X as defined in any of claims 6-7 comprising the following steps:
a) formation of a halo or alkyl ester of a squaric acid derivative Ic, as represented by Scheme VIII
1a 1b 1c
(Scheme VIII)
Hal = Br, I, Cl, Tosyl R being any alkyl group, preferably a Q - C4 alkyl, R31, R33 and R34 being as defined in any of claims 1-5,
and bl) deprotection of alkyl ester to hydroxyl group, as represented by scheme IX
(Scheme IX)
followed subsequently by a condensation reaction between intermediate Id and compound Ie, as represented by Scheme X
1d 1e i
(Scheme X)
or
b2) a direct reaction between product from step a) and compound Ie, as represented by Scheme XI
1c 1e i
(Scheme XI)
9. An electronic device comprising a dye as defined in any of claims 1-5.
10. The device according to claim 9, which is a solar cell, preferably a dye-sensitized solar cell.
1 1. The device according to claim 10, being a dye-sensitized solar cell, said dye being chemisorbed to a photoactive semiconductor porous material in said dye-sensitized solar cell.
12. The device according to any of claims 9-1 1 , further comprising at least one other dye.
13. The device according to claim 12, wherein said at least one other dye is red-dye or black- dye or a combination of the two.
14. The device according to any of claims 9-13, wherein said dye is present in solution or wherein said dye is present in a film.
15. Use of a dye as defined in any of claims 1 - 5 as sensitizer in a dye-sensitized solar cell.
16. Use according to claim 15, together with at least one other dye.
17. Use according to claim 16, wherein said at least one other dye is a dye as defined in any of claims 1-5, or red-dye or black-dye or a combination of the two.
18. A compound represented by one of the following formulae
1d 1β 
1 
4 wherein R3I-R36, R, Hal and said conjugated system are as defined in any of claims 7-8.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010530352A JP5501239B2 (en) | 2007-10-25 | 2008-10-27 | Squarylium dyes containing anchor groups |
| EP08842861A EP2212895A1 (en) | 2007-10-25 | 2008-10-27 | Squarylium dyes including an anchoring group |
| US12/739,573 US8445697B2 (en) | 2007-10-25 | 2008-10-27 | Squarylium dyes including an anchoring group |
| CN2008801128842A CN101836275B (en) | 2007-10-25 | 2008-10-27 | Squarylium dyes including an anchoring group |
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|---|---|---|---|
| EP07020925.9 | 2007-10-25 | ||
| EP07020925A EP2053618A1 (en) | 2007-10-25 | 2007-10-25 | A dye including an anchoring group in its molecular structure |
| EP08007856.1 | 2008-04-23 | ||
| EP08007856A EP2112671A1 (en) | 2008-04-23 | 2008-04-23 | A dye including an anchoring group in its molecular structure |
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| PCT/EP2008/009075 WO2009053108A1 (en) | 2007-10-25 | 2008-10-27 | A dye including an anchoring group in its molecular structure |
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| US (2) | US8445697B2 (en) |
| EP (2) | EP2212895A1 (en) |
| JP (2) | JP5501239B2 (en) |
| CN (2) | CN101836275B (en) |
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| EP2362884B1 (en) * | 2008-10-27 | 2017-08-02 | Sony Corporation | A dye comprising a chromophore to which an acyloin group is attached |
| US20140295102A1 (en) * | 2011-04-12 | 2014-10-02 | Aldo Di Carlo | Sintering process of metal oxide based formulations |
| US8722905B2 (en) | 2012-03-28 | 2014-05-13 | Industrial Technology Research Institute | Dyes and photoelectric conversion devices containing the same |
| EP2940781A4 (en) * | 2012-12-28 | 2016-08-17 | Adeka Corp | Loaded body and photoelectric conversion element |
| WO2018020518A1 (en) * | 2016-07-28 | 2018-02-01 | Council Of Scientific And Industrial Research | Squaraine dyes and applications thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5501239B2 (en) | 2014-05-21 |
| US20100300521A1 (en) | 2010-12-02 |
| EP2208212A1 (en) | 2010-07-21 |
| WO2009053108A1 (en) | 2009-04-30 |
| EP2208212B1 (en) | 2015-12-09 |
| JP2011504190A (en) | 2011-02-03 |
| CN101836275A (en) | 2010-09-15 |
| CN101836274B (en) | 2014-03-26 |
| CN101836275B (en) | 2013-11-06 |
| JP2011502187A (en) | 2011-01-20 |
| US8445697B2 (en) | 2013-05-21 |
| US20100212737A1 (en) | 2010-08-26 |
| EP2212895A1 (en) | 2010-08-04 |
| RU2010120881A (en) | 2011-11-27 |
| BRPI0818449A2 (en) | 2015-05-12 |
| RU2490746C2 (en) | 2013-08-20 |
| JP5584127B2 (en) | 2014-09-03 |
| CN101836274A (en) | 2010-09-15 |
| US8440840B2 (en) | 2013-05-14 |
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