WO2016111636A1 - Benzo[1,2-b:4,5-b]furan derivatives as ligands of ruthenium dyes and methods for obtaining thereof - Google Patents
Benzo[1,2-b:4,5-b]furan derivatives as ligands of ruthenium dyes and methods for obtaining thereof Download PDFInfo
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- WO2016111636A1 WO2016111636A1 PCT/PL2015/000206 PL2015000206W WO2016111636A1 WO 2016111636 A1 WO2016111636 A1 WO 2016111636A1 PL 2015000206 W PL2015000206 W PL 2015000206W WO 2016111636 A1 WO2016111636 A1 WO 2016111636A1
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- Prior art keywords
- formula
- ruthenium
- ligand
- complex
- bis
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- 238000000034 method Methods 0.000 title claims abstract description 109
- 239000003446 ligand Substances 0.000 title claims abstract description 81
- 229910052707 ruthenium Inorganic materials 0.000 title claims description 54
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims description 50
- 239000000975 dye Substances 0.000 title description 7
- 150000002240 furans Chemical class 0.000 title description 2
- 125000005605 benzo group Chemical group 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 10
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 7
- 239000012327 Ruthenium complex Substances 0.000 claims abstract description 5
- 230000002165 photosensitisation Effects 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 150000002148 esters Chemical class 0.000 claims description 52
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 49
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 49
- 239000000047 product Substances 0.000 claims description 49
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- -1 copper halide Chemical class 0.000 claims description 30
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 30
- 125000001931 aliphatic group Chemical group 0.000 claims description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 28
- 239000000539 dimer Substances 0.000 claims description 25
- 238000002955 isolation Methods 0.000 claims description 24
- 150000003462 sulfoxides Chemical class 0.000 claims description 23
- 150000002825 nitriles Chemical class 0.000 claims description 22
- ZMGMDXCADSRNCX-UHFFFAOYSA-N 5,6-dihydroxy-1,3-diazepan-2-one Chemical class OC1CNC(=O)NCC1O ZMGMDXCADSRNCX-UHFFFAOYSA-N 0.000 claims description 21
- 150000001408 amides Chemical class 0.000 claims description 21
- 150000002576 ketones Chemical class 0.000 claims description 21
- 150000003951 lactams Chemical class 0.000 claims description 21
- 150000002596 lactones Chemical class 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- 239000000543 intermediate Substances 0.000 claims description 15
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 14
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- 150000002540 isothiocyanates Chemical class 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 238000007239 Wittig reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 5
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- 229920000151 polyglycol Polymers 0.000 claims description 5
- 239000010695 polyglycol Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical compound C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 5
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 4
- 229940043279 diisopropylamine Drugs 0.000 claims description 4
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 claims description 3
- LRUNVGPYZQYWKA-UHFFFAOYSA-N 4,4-diethynyl-2-pyridin-2-yl-3H-pyridine Chemical compound C(#C)C1(CC(=NC=C1)C1=NC=CC=C1)C#C LRUNVGPYZQYWKA-UHFFFAOYSA-N 0.000 claims description 3
- UUCDFENOFAWRMR-UHFFFAOYSA-N 5-hydroxy-6-iodo-2-methyl-1-benzofuran-3-carboxylic acid Chemical compound OC=1C(=CC2=C(C(=C(O2)C)C(=O)O)C=1)I UUCDFENOFAWRMR-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910001506 inorganic fluoride Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OFDVABAUFQJWEZ-UHFFFAOYSA-N 3-pyridin-3-ylpyridine Chemical compound C1=CN=CC(C=2C=NC=CC=2)=C1 OFDVABAUFQJWEZ-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 2
- 239000003049 inorganic solvent Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 150000002941 palladium compounds Chemical group 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims 3
- LAXRNWSASWOFOT-UHFFFAOYSA-J (cymene)ruthenium dichloride dimer Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ru+2].[Ru+2].CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 LAXRNWSASWOFOT-UHFFFAOYSA-J 0.000 claims 1
- 101100459438 Caenorhabditis elegans nac-1 gene Proteins 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 150000005826 halohydrocarbons Chemical class 0.000 claims 1
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 claims 1
- 230000008033 biological extinction Effects 0.000 abstract description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 29
- 238000010521 absorption reaction Methods 0.000 description 13
- XELZGAJCZANUQH-UHFFFAOYSA-N methyl 1-acetylthieno[3,2-c]pyrazole-5-carboxylate Chemical compound CC(=O)N1N=CC2=C1C=C(C(=O)OC)S2 XELZGAJCZANUQH-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 8
- 125000003158 alcohol group Chemical group 0.000 description 7
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 230000008034 disappearance Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 238000004611 spectroscopical analysis Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- JIWVHJAIMWCERM-UHFFFAOYSA-N 2,3-dichloro-1-methyl-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(C)C(Cl)=C1Cl JIWVHJAIMWCERM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- JGBZTJWQMWZVNX-UHFFFAOYSA-N palladium;tricyclohexylphosphane Chemical compound [Pd].C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 JGBZTJWQMWZVNX-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 150000003567 thiocyanates Chemical class 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 1
- IAFFEFPJCKQBKK-UHFFFAOYSA-N 2,3-dichloro-1-methyl-4-propan-2-ylbenzene;ruthenium Chemical compound [Ru].CC(C)C1=CC=C(C)C(Cl)=C1Cl IAFFEFPJCKQBKK-UHFFFAOYSA-N 0.000 description 1
- NPYGILQVQLESKX-PHEQNACWSA-N 4-[(e)-2-(4-hexoxyphenyl)ethenyl]-2-[4-[(e)-2-(4-hexoxyphenyl)ethenyl]pyridin-2-yl]pyridine Chemical compound C1=CC(OCCCCCC)=CC=C1\C=C\C1=CC=NC(C=2N=CC=C(\C=C\C=3C=CC(OCCCCCC)=CC=3)C=2)=C1 NPYGILQVQLESKX-PHEQNACWSA-N 0.000 description 1
- KIIHBDSNVJRWFY-UHFFFAOYSA-N 4-bromo-2-(4-bromopyridin-2-yl)pyridine Chemical compound BrC1=CC=NC(C=2N=CC=C(Br)C=2)=C1 KIIHBDSNVJRWFY-UHFFFAOYSA-N 0.000 description 1
- VRZUWDJLVOHARA-UHFFFAOYSA-N 4-ethynyl-2-(4-ethynylpyridin-2-yl)pyridine Chemical compound C#CC1=CC=NC(C=2N=CC=C(C=2)C#C)=C1 VRZUWDJLVOHARA-UHFFFAOYSA-N 0.000 description 1
- VHJFWJXYEWHCGD-UHFFFAOYSA-N 4-nonyl-2-(4-nonylpyridin-2-yl)pyridine Chemical compound CCCCCCCCCC1=CC=NC(C=2N=CC=C(CCCCCCCCC)C=2)=C1 VHJFWJXYEWHCGD-UHFFFAOYSA-N 0.000 description 1
- JSVSZYZARGPNLA-UHFFFAOYSA-N 4-tridecyl-2-(4-tridecylpyridin-2-yl)pyridine Chemical compound CCCCCCCCCCCCCC1=CC=NC(C=2N=CC=C(CCCCCCCCCCCCC)C=2)=C1 JSVSZYZARGPNLA-UHFFFAOYSA-N 0.000 description 1
- PMQFCQKIRJLFAS-UHFFFAOYSA-N 5-hydroxy-2-methyl-1-benzofuran-3-carboxylic acid Chemical compound C1=C(O)C=C2C(C(O)=O)=C(C)OC2=C1 PMQFCQKIRJLFAS-UHFFFAOYSA-N 0.000 description 1
- YULXXZVRAJVGRR-UHFFFAOYSA-N 6-bromo-5-hydroxy-2-methyl-1-benzofuran-3-carboxylic acid Chemical compound OC=1C(=CC2=C(C(=C(O2)C)C(=O)O)C=1)Br YULXXZVRAJVGRR-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000003609 aryl vinyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- QJPQVXSHYBGQGM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJPQVXSHYBGQGM-UHFFFAOYSA-N 0.000 description 1
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 1
- 230000000886 photobiology Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
Definitions
- the present invention relates to the Iigands comprising in their structure benzodifuran moiet and ruthenium complexes constructed on the basis on said Iigands and methods for their preparing, and use for DSSC thereof.
- M. Gretzel and M.K. Nazeeruddin in US005463057A disclose a complex of two molecules of 2,2'-bipyridyl-4,4'-dicarboxylic acid (dcbpy) with ruthenium and isothiocyanate groups, having been converted into a tetrabutylammonium salt, for the purpose of improving the solubility in alcohols, water and the polar organic solvents, said complex is used as a photosensitizer of titanium oxide in the dye photovoltaic cells of DSSC type.
- dcbpy 2,2'-bipyridyl-4,4'-dicarboxylic acid
- ruthenium and isothiocyanate groups having been converted into a tetrabutylammonium salt
- the mixed ruthenium complexes which comprise two different Iigands comp!exed to the ruthenium atom are also known.
- IPCE incident photon-to-current conversion efficiency
- incorporation of the thiophene system to the bipyridyl ligand may increase energy levels of metal center and LU O orbital of the ligand. Consequently, the absorption band derived from the passage of the "charge transfer" type from metal to ligand shifts toward longer wavelengths.
- the subject of the present invention are novel ligands for the synthesis of the photosensitizing complexes of ruthenium for use in DSSC
- Ri H, alkyl, alkene, aikyne, aromatic hydrocarbon, polyglycol, organic salt (e.g. tetrabutylammonium) and inorganic salt (e.g. sodium);
- the subject of the invention are further new symmetric and asymmetric photosensitizing ruthenium complexes of the invention for use DSSC wherein
- the subject of the invention is a method for the preparing a 6,6'-([2,2'- bipyridine]-4,4'-diyl)bis(2-methylbenzo[1 ,2-6:4, 5-6']difuran-3-carboxylic) acid ligand (1) of formula !
- esters and salts thereof wherein said method comprises the steps of obtaining ligand 1 using the Sonogashira reaction of 4,4'-dihalo-2,2'-bipyridine with ethynyltrimethylsilane in a solvent, in the presence of a palladium catalyst, with or without addition of a phosphine, in the presence of copper halide and amine as a base; wherein removing the trimethylsilyl groups in the intermediate product is carried out without isolation thereof, with the use of fluoride or alkaline hydrolysis in a mixture of water and alcohol or tetrahydrofuran, reacting resulted 4,4-diethynyl-2,2'-bipyridine without isolation thereof with an ester of 5- hydroxy-6-haIo-2-methyibenzofuran-3-carboxylic acid at room temperature or higher temperature to yield the Iigand of formula I, hydrolyzing thereof, if necessary, under basic or acid conditions and isolating using
- Suitable solvents are aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrite, ether, alcohol, ketone, ester or lactone, N- substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents.
- the solvent is selected from toluene, xylene, tetrahydrofuran, dimethyl sulfoxide, acetonitrile or 1 ,4-dioxane or mixture thereof.
- the catalyst used according to the invention is a palladium compound selected from the group consisting of paliadium(!l) dihalides, palladium(ll) acetate, palladium(il) sulfate, bis(triphenylphosphine)paliadium(l[) dichloride, bis(tricyclopentyIphosphine)palladium(ll) dichloride, bis(tricyclohexylphosphine)- palladium(ll), bis(dibenzylideneacetone)palladium(0), tetrakis(triphenylphosphine)palladium(0), preferably [1 ,1'-bis (dipheny!phosphino) ferrocene]dichloropalladium(ll).
- reaction is carried out with or without addition of aromatic or nonaromatic phosphine.
- the reaction is carried out with the addition of a copper halide, preferably copper iodide.
- the reaction is carried out in the presence of aliphatic, alicyclic, aromatic, heterocyclic amine, preferably diisopropylamine, at room temperature or higher temperature.
- the method comprises the step of removing the trimethy!silyl groups from the intermediate without isolation thereof using organic or inorganic fluorides, or alkaline hydrolysis in a mixture of water and alcohol or tetrahydrofuran, preferably tetrabutylammonium fluoride.
- the method comprise step of reacting in the same flask resulting 4,4'-diethynyl-2,2'-bipyridine, without isolation thereof, with an ester of 5-hydroxy-6- halo-2-methyl-benzofuran-3-carboxylic acid. More preferably, reacting the resulting 4 J 4'-diethynyl-2,2'-bipyridine with 5- hydroxy-6-bromo-2-methyl-benzofuran-3-carboxylic acid ester or 5-hydroxy-6-iodo-2- methyi-benzofuran-3-carboxylic acid ester.
- reaction of 4,4'-diethinylo-2,2 , -bipyridine with 5-hydroxy-6-iodo-2-methyl- benzofuran-3-carboxylic acid ester is carried out at room temperature or higher temperature, preferably at 80°C.
- the subject of the invention is also a method for the preparing 6,6'-((1 ,1')- [3,3 , -bipyridine]-4,4'-diyibis(etheno-2,1-diyl))bis(2-methylobenzo[1 ,2-b:4,5- ⁇ ']-difuran- 3,7-dicarboxylic) acid ligand (2) of Formula II, according to the invention, and esters and salts thereof, wherein the method comprises the steps of obtaining the ligand 2 using the Wittig reaction of [2,2'-bipyridine]-4,4'-carbaldehyde with ((3,7- bis(alkoxycarbonyl)-6-methylbenzo[1 ,2-/):4,5-iti]difuran-2-yl)methyl)triphenyi- phosphonium halide in an organic solvent in the presence of a base, at room temperature or higher temperature, if necessary, hydrolyzing thereof under basic or acidic conditions and is
- the suitable solvents are alcohol, hydrocarbon, aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably isopropanol.
- the sutiabte base are hydroxides of alkali metals, preferably lithium hydroxide or a hydrate thereof.
- the reaction is carried out at room or elevated temperature, preferably at the reflux temperature of isopropanol.
- the further subject of the invention is a method for the preparing 2-((5H- cyclopenta[1 ,2-0:5, 4-0']dipyridin-5-ylidene)methyl)-6-methylbenzo[1 ,2-jb:4,5-b']difuran- 3,7-dicarboxy!ic acid ligand (3) of the formula III according to the invention and esters and salts thereof, wherein the method comprises the steps for obtaining a ligand 3 using the Wittig reaction of 5H-cyclopenta[1 ,2-j :5,4-j ]dipyridin-5-one with ((3,7- bis(alkoxycarbonyl)-6-methylbenzo[1 ,2-0:4,5-/ ']difuran-2-yl)methyl)
- tritriphenylphosphonium halide in a solvent, in the presence of a base, at room temperature or higher temperatureand which, if necessary, hydrolyzing thereof under basic or acidic conditions and isolating using a known method.
- the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably isopropanol.
- the suitable base is one of the hydroxides of alkali metals, preferably lithium hydroxide or a hydrate thereof.
- the reaction is carried out at room or elevated temperature, preferably at the reflux temperature of isopropanol.
- the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium(ll).
- the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably N,N-dimethylformamide.
- the complex 4 is obtained in one process, without isolation of intermediates.
- the reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
- the source of ruthenium is a dimer of dichloro(p-cymene) ruthenium(l!).
- the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic haiohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably N,N-dimethylformamide.
- the complex 5 is obtained in one process, without isolation of intermediates.
- the reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
- the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium(ll).
- the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic haiohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably N,N-dimethylformamide.
- the complex 6 is obtained in one process, without isolation of intermediates.
- the reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
- the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium (II).
- the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably the suitable solvent is W,N-dimethylformamide.
- the complex 7 is obtained in one process, without isolation of intermediates.
- the reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
- the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium(ll).
- the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably ⁇ , ⁇ -dimethylformamide.
- the complex 8 can be obtained in one process, without isolation of
- reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
- the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium(ll).
- the suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably A/,/V-dimethylformamide.
- the complex 9 is obtained in one process, without isolation of intermediates.
- the reaction is carried out at room or elevated temperature, preferably at a temperature of 140- 50°C.
- Developed symmetric and asymmetric ruthenium complexes 3-9 show the absorption of visible light and UV with high molar extinction coefficients and can be used as dye for the production of DSSC (Dye-Sensitized Solar Cells). The products are stable in air and after exposure to sunlight.
- the precursors for the synthesis of ligand 1 are the esters of 5-hydroxy-6- haio-2-methyl-benzofuran-3-carboxylic acid obtained in known bromination or iodination reactions of 5-hydroxy-2-methyl-benzofuran-3-carboxylic acid ester, wherein said ester can be obtained in known reaction of p-£>enzoquinone with ethyl acetoacetate in ethanol, treated by known transesterification reaction of an aliphatic, unsaturated, cyclic, aromatic alcohol, polyglycol, in acidic or alkaline conditions and separated by a known method, ethyny!trimethylsilane and 4,4'-dihalogeno-2,2'- bipyridine.
- the precursors for the synthesis of !igand 2 are following: known 2,2'- bipyridine-4,4'-dikarboaldehyd and salts of ((3,7-bis(alkoxycarbonyl)-6-methylbenzo [1 , 2-0:4, 5-b]difuran-2-yl)methyl)triphenylphosphonium obtained by a known method with a known esters of 2-(halomethyl)-6-methylbenzo[1 ,2 ⁇ jb:4,5-0']difuran-3,7- dicarboxy!ic acid by reaction with triphenylphosphine in an organic solvent.
- the precursors for the synthesis of ligand 3 are following: known 5H- cy openta-[1 ,2-6:5, 4-/b]dipyridin-5-one and salts of ((3,7 ⁇ bis(alkoxycarbonyl)-6- methyl[1 ,2b:4,5-jb]difuran-2-yl)methyl)triphenylphosphonium obtained by a known method with a known esters 2-(halomethyl)-6-methylbenzo[1 ,2-£>:4,5-J_>']difuran-3,7- dicarboxylic acid by reaction with triphenylphosphine in an organic solvent.
- the precursors for the synthesis of complexes 4, 6, 8 are following: compounds 1-3, ruthenium(lil) chloride or a dimer of dichloro(p-cymene)ruthenium(!l), 2,2 , -bipyridine-4,4 , -dicarboxylic acid and inorganic thiocyanate.
- the precursors for the synthesis of complexes 5, 7, 9 are following: the compounds 1-3, ruthenium(III) chloride or a dimer of dichloro(p-cymene)ruthenium(ll) and the inorganic thiocyanate.
- a method for the preparing of 6,6 , -([2,2 , -bipyndine] ⁇ 4,4 , -diy])b!s (2- methylbenzo[1 , 2-0:4, 5-i>']difuran-3-carboxylic) acid (1) consists in Sonogashiry reacting 4,4'-dihalogeno-2,2'-bipyridine with ethynyltrimethylsilane in organic solvent such as aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, in the presence of a palladium catalyst selected from the group consisting of palladium(ll) dihalides, palladium(li) acetate, palladium(ll) sulf
- Trimethylsilyl group in the intermediate are removed with the use of organic or inorganic fluorides or alkaline hydrolysis in mixture of water and alcohol or tetrahydrofuran.
- the resulting 4,4-diethynyl ⁇ 2,2'-bipyndine without isolation is reacted with an ester of 5-hydroxy-6-halo-2-methyi-benzofuran-3- carboxy!ic acid at room temperature or higher temperature to yield the ligand of formula I, which is hydrolyzed under basic or acidic conditions, and if necessary, isolating thereof using a known method.
- a method for obtaining of symmetrical ruthenium complexes 5, 7, 9 comprises reaction of compounds 1-3 with ruthenium(lll) chloride, or dichloro(p- cymene)ruthenium(ll) dimer and the inorganic thiocyanates in an inorganic solvent such as an aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably in N,A/-dimethylformamtde, at room temperature or higher temperature.
- an inorganic solvent such as an aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N-substituted lact
- a method for the preparing asymmetric ruthenium complexes 4, 6, 8 comprise reacting of compounds 1-3 with 2,2'-bipyridine-4 ! 4'-dicarboxylic acid, ruthenium(lll) chloride, or a dimer of dichloro(p-cymene)ruthenium(l! and inorganic thiocyanates in organic solvent such as aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic ha!ohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably N,A/-dimethylformamide, at room temperature or higher temperature.
- organic solvent such as aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic ha!ohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N
- 4,4'-Dihalogeno-2,2'-bipyridine is subjected to a Sonogashira reaction with ethynyltrimethylsilane in dry toluene in the presence of [1 ,1 '-bis(diphenylphosphino)- ferrocene]dichloropailadium(ll), copper iodide, and diisopropylamine as a base, at room temperature or higher temperature. Trimethylsilyl group in the intermediate product is removed with tetrabutylammonium fluoride.
- ligands 1-3 are reacting with a dimer of dichloro(p- cymene)ruthenium (II), with or without addition of 2,2 , -bipyrsdyl-4,4'-dicarboxy!ic acid, in the dark in ⁇ /,/V-dimethylformamide, at a temperature of 140- 50°C, and then without isolation of the ammonium thiocyanate.
- the product is isolated using filtration, dried under reduced pressure and purified on a Sephadex LH-20, eluted with N,N- dimethylformamide.
- ruthenium complexes are insoluble in alcohols, acetonitrile, valeronitrile and other organic solvents with the exception of /V,W-dimethylformamide and dimethyisuifoxide.
- they are converted into tetrabutylammonium salts by titration with tetrabutylammonium hydroxide in ethanol to pH> 7, filtered and then titrated with dilute nitric acid(V) to pH 4-6, then ethanol was removed, washed with water at pH 4-6 and dried in vacuo over phosphorus pentoxide or in the air.
- the so obtained salts are brown or black solids exhibiting absorption in the UV-Vis range both in the crystalline state and in solution.
- the products are stable in air and after exposure to sunlight.
- Ruthenium complexes 4-9 in form of the tetrabutylammonium salts in the ethanol solution at a concentration of 1 *10 ⁇ 4 mol/dm 3 show absorption of electromagnetic radiation in the UV-Vis range.
- Ligand 1 according to the invention is prepared by three-step synthesis performed in a single process, without isolation of intermediates.
- Ethynyltrimethylsilane (1.2766 g, 13 mmol) in dry toluene (5 mL) was added and heated at 80°C under a nitrogen 1.2766 atmosphere up to disappearance of etynylotrimethylsilane according to GC (2 h). After cooling to the room temperature, 1 solution of tetrabutyiammonium fluoride in dry tetrahydrofuran (13 mL) was added and stirred for 1 minute.
- octyl 5-hydroxy-6-iodo-2-methyi- benzofuran-3-carboxylate (4.3040 g, 10 mmol) in dry toluene (50 mL) was added and stirred at 80 D C for 14 hours, it was allowed to cool to room temperature, water (40 mL) was added and the precipitate was filtered off on a Buchner funnel. The precipitate was transferred to the 250 mL flask and water (50 mL) and diethyl ether (50 mL) were added and stirred for 10 minutes. The precipitate was again filtered on a Buchner funnel and dried in vacuum over phosphorus pentoxide to yield 3.8870 g (96%) of pure product. M.p.
- Ligand 2 according to the invention is prepared by a one-step synthesis.
- [2,2'-Bipyridine]-4,4'- dikarboaldehyd (0.5088 g, 2.4 mmol) was added and the temperature was raised to 60°C for 5 minutes. The mixture was stirred at this temperature for 40 minutes, water (45 mL) added, filtered the resulting precipitate, which was washed with water (3x30 mL) and methanol (3 x 25 mL) and air dried to give 2.80 g of a dark orange powder. The crude product was heated in boiling p-xyiene (20 mL) containing a crystal of iodine for 1.5 hours.
- Ligand 3 of the invention is prepared by a one-step synthesis.
- Complex 4 according to the invention is prepared by a one-step synthesis.
- 2,2'-Bipyridine-4,4'-dicarboxylic acid (0.2442 g, 1 mmol) was added and stirred at 150°C for a further 4 hours.
- Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for another 4 hours. It was cooled to room temperature, the precipitate was filtered off and W,W-dimethylformamide removed using a rotary evaporator. To the residue water (100 mL) was added and the precipitate filtered. The precipitate was washed with more water (100 mL) and dried to give 0.985 g of crude product.
- the product was purified twice on Sephadex LH-20, eluted with W,W-dimethylformamide and the main band collected to yield 0.440 g (35%) of black, glossy product.
- the complex 5 of the present invention is prepared by a one-step synthesis.
- Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for another 4 hours. It was cooled to room temperature, the precipitate was filtered off and /V,/V-dimethylformamide removed using a rotary evaporator. Water (100 mL) was added to the residue and the precipitate was filtered. The precipitate was washed with more water (100 mL) and dried to give 0.985 g of crude product. The product was purified twice on Sephadex LH-20, eluted with ⁇ /,/V-dimethylformamide and the main band collected to yield 0.775 g (56%) of black, glossy product.
- Complex 6 according to the invention is prepared by a one-step synthesis.
- 2,2'-Bipyridine-4,4'- dicarboxylic acid (0.2442 g, 1 mmol) was added and stirred at 150°C for 4 hours.
- Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for a further 4 hours.
- Mixture was cooled to room temperature, the precipitate was filtered off and N,W-dimethylformamide removed using a rotary evaporator. Water (100 mL) was added to the residue and the precipitate filtered. The precipitate was washed with more water (100 mL) and dried to give 1 .182 g of crude product.
- the product was purified twice on Sephadex LH-20, eluted with /V-dimethylformamide and the main band collected to yield 0.834 g (51%) of b!ack, glossy product.
- the resulting precipitate was washed with water at pH 5.2 and dried to give the tetrabutyiammonium salt as a black powder, M.p.> 300°C.
- Complex 7 according to the invention is prepared by a one-step synthesis.
- Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for another 4 hours. The mixture was cooled to room temperature, the precipitate was filtered off and N,N- dimethylformamide removed using a rotary evaporator. Water (100 mL) was added to the residue and the precipitate filtered off. The precipitate was washed with more water (100 mL) and dried to give 1.305 g of crude product. The product was purified twice on Sephadex LH-20, eluted with ⁇ /, ⁇ -dimethylformamide and the main band collected, yielding 0.9150 g (59%) of black, glossy product.
- Complex 8 is prepared by a one-step synthesis.
- Dinner dichloro(p-cymene)ruihenium (il) (0.1531 g, 0.25 mmol) and ester octyl ester 2-((5H-cyclopenta[ ,2 ⁇ 0:5,4"i ']dipirydyn-5-ylidene)methyl)-6-methyibenzo[1 ,2- 0:4,5-0']difuran-3,7-dicarboxylic (0.3314 g, 0.5 mmol) in dry /V,A/-dimethylformamide (20 mL) was heated in the dark at 150°C for 2 hours, monitoring the disappearance of substrate using a UV-Vis spectrometry.
- the product was purified twice on Sephadex LH- 20, eiuted with N,/V-dimethylformamide and the main band collected to yield 0.206 g (37%) of black, glossy product.
- Complex 9 according to the invention is prepared by a one-step synthesis.
- Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for a further 4 hours. The mixture was cooled to room temperature, the precipitate was filtered off and N,N- dimethylformamide removed using a rotary evaporator. Water (100 mL) was added to the residue and the precipitate filtered. The precipitate was washed with more water (100 mL) and dried to give 0.872 g of crude product. The product was purified twice on Sephadex LH-20, eluted with ⁇ /,/V-dimethyl-formamide and the main band collected, yielding 0.6237 g (57%) of black, glossy product.
Abstract
The present invention relates to a novel ligand for the synthesis of the photosensitizer ruthenium complexes for uses in DSSC, wherein said ligand comprise in their structure benzodifuran moiety bound directly or by a multiple bond with the 2,2'-bipyridine system in positions 4,4' or fluorene system and methods for preparing of said ligand. The subject of the invention is also a new symmetric or asymmetric photosensitizing ruthenium complex for use in DSSC derived from said ligand and methods for preparation of said complex. The resulting complexes have high molar extinction coefficients in the range of visible light and are stable in air environment and after exposure to sunlight, and may be used for the producing of Dye- Sensitized Solar Cells (DSSC). Developed methods are advantageous due to the mild reaction conditions, high repeatability and moderation or high yields.
Description
Benzofl
derivatives as iigands of ruthenium dyes and methods for obtaining thereof
The present invention relates to the Iigands comprising in their structure benzodifuran moiet and ruthenium complexes constructed on the basis on said Iigands and methods for their preparing, and use for DSSC thereof.
M. Gretzel and M.K. Nazeeruddin in US005463057A disclose a complex of two molecules of 2,2'-bipyridyl-4,4'-dicarboxylic acid (dcbpy) with ruthenium and isothiocyanate groups, having been converted into a tetrabutylammonium salt, for the purpose of improving the solubility in alcohols, water and the polar organic solvents, said complex is used as a photosensitizer of titanium oxide in the dye photovoltaic cells of DSSC type.
The mixed ruthenium complexes which comprise two different Iigands comp!exed to the ruthenium atom are also known. M.S. Zakeeruddin, MK Nazeeruddin, M. Graetzel et a!. in Langmuir 2002, 18, 952, described mixed dyes formed from a single dcbpy molecule and single molecule of 4,4'-ditridecyl-2,2'- bipyridine, 4-methyl-4'~hexadecyl-2,2'-bipyridine or 4-methyl-4,-(2-dodecyltetradecyl)- 2,2'-bipyridine. These dyes have shown IPCE (incident photon-to-current conversion efficiency) of 80% and high desorption stability from the surface of titanium oxide caused by water, so that they can be used in combination with a water-based electrolytes.
P. Wang, S.M. Zakeeruddin, M.K. Nazeeruddin, M. Gratzei, et ai. in Nat. Mater. 2003, 20, 402, describe amphiphilic dye Z907 comprising one dcbpy ligand and one 4,4'-dinonyl-2,2'-bipyridine ligand having similar effect. Then, P. Wang, C. Klein, R. Humphry-Baker, S.M. Zakeeruddin, and M. Gratzei, in J. Am. Chem. Soc. 2005, 127, 808, describe heteroleptic ruthenium complex, designed with symbol K-19, comprising in addition to dcbpy an aryl-viny! ligand 4,4'-bis((E)-4-(hexyloxy)styryl)- 2,2'-bipyridine, which due to the extended system of coupled π bonds show increased absorption of visible light compared to those known in the state of the art.
M.K. Nazeeruddin, M. Gratzei et al. in Journal of Photochemistry and Photobiology A: Chemistry 2007, 185, 331 also presented similar complexes, called
N945, and K9 and K23, described in J. Phys. Chem. C, 2009, 113:1998, which show a much higher molar extinction coefficient compared to complexes without a conjugated bond system in one of the ligands as well as a shorter lifetime of electrons and rapid recombination.
C.Y. Chen, S.J. Wu, C.G. Wu, J.G. Chen and K.-C. Ho in Angew. Chem. 2006, 118, 5954, describe a ruthenium complex CYC-B1 , consisting of a single dcbpy iigand and single ligand 4,4'-bis(5'-octyl-[2,2'-bithiophene3-5-yl)-2,2'-bipyridine. Due to the aromatic conjugated system containing an aikyl-bithiophen group, similarly as described above aryl-vinyl systems, this ligand makes the ruthenium complex to be characterized by the high value of the molar extinction coefficient. Moreover incorporation of the thiophene system to the bipyridyl ligand may increase energy levels of metal center and LU O orbital of the ligand. Consequently, the absorption band derived from the passage of the "charge transfer" type from metal to ligand shifts toward longer wavelengths.
Similar complexes comprising thiophene derivatives were described by P. Gao, M. Gratzel et al. (Chem. Commun., 2008, 2635 and J. Am. Chem. Soc. 2008, 130, 10720), C.Y. Chen, M. Gratzel et al. (AcsNano, 2009, 3, 3103), Q. Yu, P., Wang et al. (J. Phys. Chem. C 2009, 1 13, 14559), Y. Cao, P. Wang et al. (J. Phys. Chem. C. 2009, 1 13, 6290).
F. Gao, M. Gratzel et al., in J. Am. Chem. Soc. 2008, 130, 10720 describe, in addition to the thiophene derivative, also furan derivatives. The state of the art does not, however, comprise any teaching on ligands substituted in positions 4,4' of the 2,2'-bipyridine with benzodifuran and benzofuran groups which show absorption of UV-Vis radiation with high molar extinction coefficients.
The subject of the present invention are novel ligands for the synthesis of the photosensitizing complexes of ruthenium for use in DSSC
wherein said ligand has formula I, wherein Ri = H, alkyl, alkene, aikyne, aromatic hydrocarbon, polyglycol, organic salt (eg. tetra-butylammonium) and inorganic salt (e.g. sodium);
formula II, wherein Ri = H, alkyl, alkene, aikyne, aromatic hydrocarbon, polyglycol, organic salt (e.g. tetrabutylammonium) and inorganic salt (e.g. sodium);
Formula !
Formula l!l
The subject of the invention are further new symmetric and asymmetric photosensitizing ruthenium complexes of the invention for use DSSC wherein
the complex has formula IV, wherein U = ligand of formula I, L2 = !igand of formula V;
formula IV, wherein Li = L2 = ligand of formula I;
formula IV, wherein U = ligand of formula II, L2 = ligand of formula V;
formula IV, wherein U = L2 = ligand of formula II;
formula IV, wherein U = ligand of formula III, L2 = ligand of formula V;
formula IV, wherein L-i = L2 = ligand of formula III.
Formula V
The subject of the invention is a method for the preparing a 6,6'-([2,2'- bipyridine]-4,4'-diyl)bis(2-methylbenzo[1 ,2-6:4, 5-6']difuran-3-carboxylic) acid ligand (1) of formula ! according to the invention, esters and salts thereof, wherein said method comprises the steps of obtaining ligand 1 using the Sonogashira reaction of 4,4'-dihalo-2,2'-bipyridine with ethynyltrimethylsilane in a solvent, in the presence of a palladium catalyst, with or without addition of a phosphine, in the presence of copper halide and amine as a base; wherein removing the trimethylsilyl groups in the
intermediate product is carried out without isolation thereof, with the use of fluoride or alkaline hydrolysis in a mixture of water and alcohol or tetrahydrofuran, reacting resulted 4,4-diethynyl-2,2'-bipyridine without isolation thereof with an ester of 5- hydroxy-6-haIo-2-methyibenzofuran-3-carboxylic acid at room temperature or higher temperature to yield the Iigand of formula I, hydrolyzing thereof, if necessary, under basic or acid conditions and isolating using a known method.
Suitable solvents are aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrite, ether, alcohol, ketone, ester or lactone, N- substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents. Preferably the solvent is selected from toluene, xylene, tetrahydrofuran, dimethyl sulfoxide, acetonitrile or 1 ,4-dioxane or mixture thereof.
The catalyst used according to the invention is a palladium compound selected from the group consisting of paliadium(!l) dihalides, palladium(ll) acetate, palladium(il) sulfate, bis(triphenylphosphine)paliadium(l[) dichloride, bis(tricyclopentyIphosphine)palladium(ll) dichloride, bis(tricyclohexylphosphine)- palladium(ll), bis(dibenzylideneacetone)palladium(0), tetrakis(triphenylphosphine)palladium(0), preferably [1 ,1'-bis (dipheny!phosphino) ferrocene]dichloropalladium(ll).
The reaction is carried out with or without addition of aromatic or nonaromatic phosphine.
The reaction is carried out with the addition of a copper halide, preferably copper iodide.
The reaction is carried out in the presence of aliphatic, alicyclic, aromatic, heterocyclic amine, preferably diisopropylamine, at room temperature or higher temperature.
The method comprises the step of removing the trimethy!silyl groups from the intermediate without isolation thereof using organic or inorganic fluorides, or alkaline hydrolysis in a mixture of water and alcohol or tetrahydrofuran, preferably tetrabutylammonium fluoride.
Preferably, the method comprise step of reacting in the same flask resulting 4,4'-diethynyl-2,2'-bipyridine, without isolation thereof, with an ester of 5-hydroxy-6- halo-2-methyl-benzofuran-3-carboxylic acid.
More preferably, reacting the resulting 4J4'-diethynyl-2,2'-bipyridine with 5- hydroxy-6-bromo-2-methyl-benzofuran-3-carboxylic acid ester or 5-hydroxy-6-iodo-2- methyi-benzofuran-3-carboxylic acid ester.
Most preferably, the resulting 4,4'-diethynyl-2,2'-bipyrid!ne is reacted with 5- hydroxy-6-iodo-2-methyl-benzofuran-3-carboxyiic acid ester.
The reaction of 4,4'-diethinylo-2,2,-bipyridine with 5-hydroxy-6-iodo-2-methyl- benzofuran-3-carboxylic acid ester is carried out at room temperature or higher temperature, preferably at 80°C.
The subject of the invention is also a method for the preparing 6,6'-((1 ,1')- [3,3,-bipyridine]-4,4'-diyibis(etheno-2,1-diyl))bis(2-methylobenzo[1 ,2-b:4,5-^']-difuran- 3,7-dicarboxylic) acid ligand (2) of Formula II, according to the invention, and esters and salts thereof, wherein the method comprises the steps of obtaining the ligand 2 using the Wittig reaction of [2,2'-bipyridine]-4,4'-carbaldehyde with ((3,7- bis(alkoxycarbonyl)-6-methylbenzo[1 ,2-/):4,5-iti]difuran-2-yl)methyl)triphenyi- phosphonium halide in an organic solvent in the presence of a base, at room temperature or higher temperature, if necessary, hydrolyzing thereof under basic or acidic conditions and isolating using a known method.
The suitable solvents are alcohol, hydrocarbon, aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably isopropanol.
The sutiabte base are hydroxides of alkali metals, preferably lithium hydroxide or a hydrate thereof.
The reaction is carried out at room or elevated temperature, preferably at the reflux temperature of isopropanol.
The further subject of the invention is a method for the preparing 2-((5H- cyclopenta[1 ,2-0:5, 4-0']dipyridin-5-ylidene)methyl)-6-methylbenzo[1 ,2-jb:4,5-b']difuran- 3,7-dicarboxy!ic acid ligand (3) of the formula III according to the invention and esters and salts thereof, wherein the method comprises the steps for obtaining a ligand 3 using the Wittig reaction of 5H-cyclopenta[1 ,2-j :5,4-j ]dipyridin-5-one with ((3,7- bis(alkoxycarbonyl)-6-methylbenzo[1 ,2-0:4,5-/ ']difuran-2-yl)methyl)
tritriphenylphosphonium halide in a solvent, in the presence of a base, at room
temperature or higher temperatureand which, if necessary, hydrolyzing thereof under basic or acidic conditions and isolating using a known method.
The suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably isopropanol.
The suitable base is one of the hydroxides of alkali metals, preferably lithium hydroxide or a hydrate thereof.
The reaction is carried out at room or elevated temperature, preferably at the reflux temperature of isopropanol.
The still further subject of the invention is method for the preparing of c/'s- bis(isothiocyanate)(6,6'-([2,2'-bipyridine]-4,4'-diyI)bis(2-methylbenzo[1 ,2-0:4,5- £),]difuran-3-karboksyio)){2,2'-bipyridyl-4,4'-dikarboksylo)ruthenium([l) complex (4) of formula IV, wherein l_i = ligand of formula I, L2 = ligand of formula V, according to the invention, and esters and salts thereof, wherein method for obtaining the complex 4 comprises step of reacting ruthenium(HI) chloride or a dimer of dichloro(p- cymene)ruthenium(ll) with ligand 1 , 2,2'-bipyridine-4,4'-dicarboxylic acid and inorganic thiocyanate in a solvent and isolating the product using a known manner.
Preferably, the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium(ll).
The suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably N,N-dimethylformamide.
The complex 4 is obtained in one process, without isolation of intermediates.
The reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
The further subject of the invention is a method for the preparing of c/s- bis{isothiocyanate)bis(6,6'-([2,2,-bipyridine]-4,4,-diyl)bis(2-methylbenzo[1 , 2-0:4,5- jb']difuran-3-karboksylo))ruthenium(ll) complex (5) having the formula IV, wherein l_i = L2 = ligand of formula I according to the invention and esters and salts thereof, wherein the method comprises the step of obtaining the complex 5 by reacting
ruthenium(lll) chloride or a dimer of dichloro(p-cymene) ruthenium(il) with Sigand 1 and inorganic thiocyanate in a solvent and isolating the product using a known manner.
Preferably, the source of ruthenium is a dimer of dichloro(p-cymene) ruthenium(l!).
The suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic haiohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably N,N-dimethylformamide.
The complex 5 is obtained in one process, without isolation of intermediates.
The reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
The still further subject of the invention is a method for the preparing of c/s- bis(isothiocyanate)(6I6'-((1 ,1 [3,3'-bipy dine]-4,4,-diylbis(eteno-2, 1-diyl))bis(2- methylbenzo[1 ,2-6:4,5-0,]difuran-3,7-dikarboksylo))(2,2'-bipyridyl-4,4'- dikarboksylo)ruthenium(il) complex (6) of formula IV, wherein l_i = ligand of formula II, l_2 = ligand of formula V, according to the invention, and esters and salts thereof, wherein the method for obtaining complex 6 comprises the step of reacting ruthenium(!ll) chloride or dimer of dichloro(p-cymene)ruthenium(ll) with ligand 2, 2,2 - bipyridine-4,4'-dicarboxylic acid and inorganic thiocyanate in a solvent and isolating the product using a known manner.
Preferably, the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium(ll).
The suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic haiohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably N,N-dimethylformamide.
The complex 6 is obtained in one process, without isolation of intermediates.
The reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
The further subject of the invention is a method for the preparing of cis- bis(isothiocyanate)bis(6,6 (1 ,1 [3,3'-bip^^^
methylbenzo[1 ,2-jb:4,5-^difuran-3(7-dikarboksylo)ruthenium(ll) complex (7) of formula IV, wherein l_i = L2 = ligand of formula II according to the invention, and esters and salts thereof, wherein method for obtaining the complex 7 comprises the step of reacting ruthenium(III) chloride or dimer of dichloro{p-cymene)ruthenium (II) with ligand 2, and inorganic thiocyanate in a solvent, and isolating the product using a known manner.
Preferably, the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium (II).
The suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably the suitable solvent is W,N-dimethylformamide.
The complex 7 is obtained in one process, without isolation of intermediates.
The reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
The further subject of the invention is a method for the preparing of cis- bis(isothiocyanate)(2-((5H-cyclopenta[1 ^-/jiS^-^Jdipirydyn-S-ylideneJmethylJ-e- methy!benzo[1 ,2-£):4,5-i),]difuran-3,7-dikarboksylo)(2,2'-bipyridyl-4,4'- dikarboksylo)ruthenium(ll) complex (8), of formula IV, wherein l_i = the ligand of formula III, L2 - a ligand of formula V; according to the invention, and esters and salts thereof, wherein the method for obtaining complex 8 comprises the step of reacting ruthenium chloride(ll l) or dimer dichloro{p-cymene)ruthenium(ll) with ligand 3 2,2'- bipyridine-4,4'-dicarboxylic and inorganic thiocyanate in a solvent and isolating the product using a known manner.
Preferably, the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium(ll).
The suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably Ν,Ν-dimethylformamide.
The complex 8 can be obtained in one process, without isolation of
intermediates.
The reaction is carried out at room or elevated temperature, preferably at a temperature of 140-150°C.
The further subject of the invention is a method for the preparing of c/s- bis(isothiocyanate)bis(2-({5H-cycIopenta[1 ^-jbiS^-b'Jdipirydyn-S-yiideneJmethylJ-e- methylbenzo[1 ,2-jf}:4,5-i ']difuran-3,7-dikarboksylo)ruthenium(ll) complex (9), of formula IV, wherein l_i = L2 = ligand of formula III, according to the invention, and esters and salts thereof, in which complex 9 is obtained by reacting ruthenium(lll) chloride or dimer dichloro(p-cymene)ruthenium(ll) ligand 3 and inorganic thiocyanate in a solvent and isolating the product using a known manner.
Preferably, the source of ruthenium is a dimer of dichloro(p-cymene)- ruthenium(ll).
The suitable solvent is an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably A/,/V-dimethylformamide.
The complex 9 is obtained in one process, without isolation of intermediates.
The reaction is carried out at room or elevated temperature, preferably at a temperature of 140- 50°C.
Description of the Invention
Developed symmetric and asymmetric ruthenium complexes 3-9 show the absorption of visible light and UV with high molar extinction coefficients and can be used as dye for the production of DSSC (Dye-Sensitized Solar Cells). The products are stable in air and after exposure to sunlight.
Developed procedures are characterized by mild reaction conditions, high repeatability and performance of the resulting products is moderate or high.
The precursors for the synthesis of ligand 1 are the esters of 5-hydroxy-6- haio-2-methyl-benzofuran-3-carboxylic acid obtained in known bromination or iodination reactions of 5-hydroxy-2-methyl-benzofuran-3-carboxylic acid ester, wherein said ester can be obtained in known reaction of p-£>enzoquinone with ethyl acetoacetate in ethanol, treated by known transesterification reaction of an aliphatic, unsaturated, cyclic, aromatic alcohol, polyglycol, in acidic or alkaline conditions and
separated by a known method, ethyny!trimethylsilane and 4,4'-dihalogeno-2,2'- bipyridine.
The precursors for the synthesis of !igand 2 are following: known 2,2'- bipyridine-4,4'-dikarboaldehyd and salts of ((3,7-bis(alkoxycarbonyl)-6-methylbenzo [1 , 2-0:4, 5-b]difuran-2-yl)methyl)triphenylphosphonium obtained by a known method with a known esters of 2-(halomethyl)-6-methylbenzo[1 ,2~jb:4,5-0']difuran-3,7- dicarboxy!ic acid by reaction with triphenylphosphine in an organic solvent.
The precursors for the synthesis of ligand 3 are following: known 5H- cy openta-[1 ,2-6:5, 4-/b]dipyridin-5-one and salts of ((3,7~bis(alkoxycarbonyl)-6- methyl[1 ,2b:4,5-jb]difuran-2-yl)methyl)triphenylphosphonium obtained by a known method with a known esters 2-(halomethyl)-6-methylbenzo[1 ,2-£>:4,5-J_>']difuran-3,7- dicarboxylic acid by reaction with triphenylphosphine in an organic solvent.
The precursors for the synthesis of complexes 4, 6, 8 are following: compounds 1-3, ruthenium(lil) chloride or a dimer of dichloro(p-cymene)ruthenium(!l), 2,2,-bipyridine-4,4,-dicarboxylic acid and inorganic thiocyanate.
The precursors for the synthesis of complexes 5, 7, 9 are following: the compounds 1-3, ruthenium(III) chloride or a dimer of dichloro(p-cymene)ruthenium(ll) and the inorganic thiocyanate.
A method for the preparing of 6,6,-([2,2,-bipyndine]~4,4,-diy])b!s (2- methylbenzo[1 , 2-0:4, 5-i>']difuran-3-carboxylic) acid (1) consists in Sonogashiry reacting 4,4'-dihalogeno-2,2'-bipyridine with ethynyltrimethylsilane in organic solvent such as aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, in the presence of a palladium catalyst selected from the group consisting of palladium(ll) dihalides, palladium(li) acetate, palladium(ll) sulfate, palladium(ll) dichloride, bis(triphenylphosphine)- palladium(l l) dichloride, bis(tricyciopentylphosphine)palladium(ll) dichloride, bis(tricyclohexylphosphine)palladium(ll), bis(dibenzylideneacetone)palladium(0), tetrakis(triphenylphosphine)palladium(0), or most preferably [1 ,1'-bis(diphenyl- phosphino)ferrocene]dichSoropalladium(ll), with or without addition of aromatic or nonaromatic phosphine, in the presence of a copper halide and amine as a base at room temperature or higher temperature. Trimethylsilyl group in the intermediate are
removed with the use of organic or inorganic fluorides or alkaline hydrolysis in mixture of water and alcohol or tetrahydrofuran. The resulting 4,4-diethynyl~2,2'-bipyndine without isolation, is reacted with an ester of 5-hydroxy-6-halo-2-methyi-benzofuran-3- carboxy!ic acid at room temperature or higher temperature to yield the ligand of formula I, which is hydrolyzed under basic or acidic conditions, and if necessary, isolating thereof using a known method.
A method for the preparing of 6,6'-((1 , 1')-[3,3'-bipyridine]-4,4'-diylbis(eteno- 2,1-diyl))bis(2-methylbenzo[1 ,2-D:4,5-o']difuran-3,7-dicarboxylic) acid (2) and esters and salts thereof, consisting in carrying the Wittig reaction of p^'-bipyridineH^'- dicarbaldehyde with ((3,7~bis(alkoxycarbonyl)-6-methyl[1 ,2b:4,5-i>]difuran-2- yl)methyl)tritnphenylphosphonium halide in an organic solvent such as an aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, alcohol, sulfoxide or a mixture of these solvents in the presence of an alkali metal hydroxide or a mixture of alkali metal hydroxides as a base at room temperature or higher temperature, which is hydrolyzed, if necessary, in basic or acidic conditions and isolated thereof using a known method.
Method for the preparing of 2-((5H-cyclopenta[1 , 2-0:5, 4-i)']dipirydyn-5- ylidene)methyl)-6"methylbenzo[1 ,2-jb:4,5-jb']difuran-3,7-dicarboxylic acid (3) and esters and salts thereof, comprising carrying out the Wittig reaction of 5H- cyclopenta[1 ,2-6:5, 4-6']dipyridin-5-one with ((3,7-bis(alkoxycarbonyl)-6-methylbenzo- [1 ,2-b:4,5-0]difuran-2-yl)methyl)tritriphenylphosphonium halide in an organic solvent such as an aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, alcohol, sulfoxide or a mixture of these solvents in the presence of an alkali metal hydroxide or a mixture of alkali metal hydroxides as a base at room temperature or higher temperature, which is hydrolyzed, if necessary, in a basic or acidic conditions and isolated thereof using a known method.
A method for obtaining of symmetrical ruthenium complexes 5, 7, 9 comprises reaction of compounds 1-3 with ruthenium(lll) chloride, or dichloro(p- cymene)ruthenium(ll) dimer and the inorganic thiocyanates in an inorganic solvent such as an aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N-substituted lactam,
amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably in N,A/-dimethylformamtde, at room temperature or higher temperature.
A method for the preparing asymmetric ruthenium complexes 4, 6, 8 comprise reacting of compounds 1-3 with 2,2'-bipyridine-4!4'-dicarboxylic acid, ruthenium(lll) chloride, or a dimer of dichloro(p-cymene)ruthenium(l!) and inorganic thiocyanates in organic solvent such as aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic ha!ohydrocarbon, nitrile, ether, alcohol, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably N,A/-dimethylformamide, at room temperature or higher temperature.
4,4'-Dihalogeno-2,2'-bipyridine is subjected to a Sonogashira reaction with ethynyltrimethylsilane in dry toluene in the presence of [1 ,1 '-bis(diphenylphosphino)- ferrocene]dichloropailadium(ll), copper iodide, and diisopropylamine as a base, at room temperature or higher temperature. Trimethylsilyl group in the intermediate product is removed with tetrabutylammonium fluoride. The resulting 4,4-diethynyl-2,2'- bipyridine without isolation, is reacting with an octyl ester of 5-hydroxy-6-iodo-2- methyl-benzofuran-3-carboxylic acid, at the temperature of 80°C to give a compound of formula I wherein Ri = octyl, with 96% yield without the need of purification by crystallization from an organic solvent or by column chromatography, mp = 212- 214°C.
[2,2'-B!pyridine]-4,4'-dikarboaldehyd subjecting to the Wittig reaction with a ((3,7-bis{alkoxycarbonyl)-6-methylbenzo[1 ,2-0:4,5-6 ]difuran-2-yl)methyl)tritriphenyl- phosphonium halide in isopropanol in the presence of lithium hydroxide at 60°C to give the compound 2, wherein Ri = octyl, in 92% yield after purification by column chromatography, mp = 126-128°C.
5H-cyclopenta[1 , 2-6:5, 4-6 'jdipyridin-5-one is subjecting to the Wittig reaction with ((3,7-bis(alkoxycarbonyl)-6-methylbenzo[ , 2-0:4, 5~6]difuran-2-yl)methyl)tritri- phenyiphosphonium halide in isopropanol in the presence of lithium hydroxide at 60°C to give the compound 2, wherein Ri = octyl, in 53% yield after purification by column chromatography, mp = 84-86°C.
Thus obtained ligands 1-3 are reacting with a dimer of dichloro(p- cymene)ruthenium (II), with or without addition of 2,2,-bipyrsdyl-4,4'-dicarboxy!ic acid,
in the dark in Λ/,/V-dimethylformamide, at a temperature of 140- 50°C, and then without isolation of the ammonium thiocyanate. The product is isolated using filtration, dried under reduced pressure and purified on a Sephadex LH-20, eluted with N,N- dimethylformamide. The yield of 4, after two purification on Sephadex LH-20: 36% (for RT = Et), 35% (R, = C8H17}. Yield 5, after two purification on Sephadex LH-20: 56% (RT = H). Yield 6, after two purification on Sephadex LH-20: 32% (for R1 = Et), 51 % (Ri = C8H 7). Yield 7, after two purification on Sephadex LH-20: 59% (R-, = H). Yield 8, after two purification on Sephadex LH-20: 37% (for Ri = Et), 37% (R-, = C8Hi7). Yield 9, after two purification on Sephadex LH-20: 57% (Ri = H). The purified compounds are black crystalline solids.
The thus obtained ruthenium complexes are insoluble in alcohols, acetonitrile, valeronitrile and other organic solvents with the exception of /V,W-dimethylformamide and dimethyisuifoxide. In order to improve solubility of the complexes, they are converted into tetrabutylammonium salts by titration with tetrabutylammonium hydroxide in ethanol to pH> 7, filtered and then titrated with dilute nitric acid(V) to pH 4-6, then ethanol was removed, washed with water at pH 4-6 and dried in vacuo over phosphorus pentoxide or in the air.
The so obtained salts are brown or black solids exhibiting absorption in the UV-Vis range both in the crystalline state and in solution. The products are stable in air and after exposure to sunlight.
Ruthenium complexes 4-9 in form of the tetrabutylammonium salts in the ethanol solution at a concentration of 1 *10~4 mol/dm3 show absorption of electromagnetic radiation in the UV-Vis range. Complex 4, for Ri = Et shows three absorption maxima Amax = 312 nm, 374 nm and 540 nm and a molar extinction coefficient ε = 32,036; 24,262 and 10,966 dm3,mol"1-cm"1, respectively. Complex 4, for R-i = C8H17 exhibits two absorption maxima Amax = 374 nm (ε = 26,697 dm3,moi"1'cm"1) and Amax = 542 nm (ε = 9,227 dm3'mor1 ,crrT1). Complex 5, for Ri = H shows three absorption maxima Amax = 308 nm (ε = 24,236 dm3,mol"1 ,cm"1) Amax - 369 nm (ε - 19,239 dm3 mol"1-cm"1) and 538 nm (ε = 8,926 dm3 mol"1 cm"1). Complex 6, for Ri = Et shows three absorption maxima Amax = 308 nm (ε - 30,249 dm3,mor1-cm"1) Amax = 403 nm (ε = 22,560 dm3,mor1 ,cm'1) and Amax = 539 nm (ε = 9,770 dm3'mol" icm"1). Complex 6, for Ri = C8Hi7 shows three absorption maxima Amax = 313 nm (ε = 31 ,820
dm3-mor1 'cm"1) Amax = 408 nm (ε = 32,070 dm3,mol"1-cm"1) and 557 nm (ε = 16,441 dm3"mor 'cm"1). Complex 7, for Ri = H shows three absorption maxima Amax = 305 nm (ε = 27,208 dm3-mor1'cm~1) Amax = 402 nm (ε = 41 ,694 dm3 moi"1 cm"1) and Amax = 559 nm (ε = 16,389 dm3'moi"1'cm"1). Complex 8, for Ri = Et, shows three absorption maxima Amax = 317 nm (ε = 17,1 10 dm3'mor1'cm"1) Amax = 403 nm (ε - 13,585 dm3,mol" 1 cm"1) and Amax = 529 nm (ε = 9,895 dmamol"1-cm"1). Complex 8, for Ri = C8H i7 shows three absorption maxima Amax = 311 nm (ε = 31 ,767 dm3,mo 1'cm"1) Amax = 416 nm (ε = 26,760 dm3'mol"1-cm"1) and 523 nm (ε = 8,354 dm3-mol" -cm"1). Complex 9, for Ri = H exhibits two absorption maxima Amax = 315 nm (ε = 19,609 dm3'mo 'cm"1) and Amax = 440 nm (ε = 37,750 dm3-mor1 cm~1).
Examples
Synthesis process according to the invention is shown in the following examples, which do not limit the scope thereof.
Exampiel :
Ligand 1 according to the invention is prepared by three-step synthesis performed in a single process, without isolation of intermediates.
Octyl 6,6'-([2,2,-bipyridine]-4,4,-diyl)bis(2-methylbenzo[1 ,2-0:4,5-i)']difuran-3- carboxyiate) (1)
4,4'-Dibromo-2,2'-bipyridine (1.5699 g, 5 mmol), [1 ,1'-bis(diphenylphosphino)- ferrocene]dichioropalladium(ll) (0.3660 g, 0.5 mmol, 10% mol), and copper iodide (0.0952 g, 0.5 mmol, 10% mol) in a 100 ml two-necked flask equipped with a reflux condenser and a magnetic stirrer were placed under nitrogen atmosphere, and dry toluene (20 mL) was added followed by diisopropylamine (10 mL, 70 mmol) and stirred for 15 minutes. Ethynyltrimethylsilane (1.2766 g, 13 mmol) in dry toluene (5 mL) was added and heated at 80°C under a nitrogen 1.2766 atmosphere up to disappearance of etynylotrimethylsilane according to GC (2 h). After cooling to the room temperature, 1 solution of tetrabutyiammonium fluoride in dry tetrahydrofuran (13 mL) was added and stirred for 1 minute. Then, octyl 5-hydroxy-6-iodo-2-methyi- benzofuran-3-carboxylate (4.3040 g, 10 mmol) in dry toluene (50 mL) was added and stirred at 80DC for 14 hours, it was allowed to cool to room temperature, water (40 mL) was added and the precipitate was filtered off on a Buchner funnel. The precipitate was transferred to the 250 mL flask and water (50 mL) and diethyl ether
(50 mL) were added and stirred for 10 minutes. The precipitate was again filtered on a Buchner funnel and dried in vacuum over phosphorus pentoxide to yield 3.8870 g (96%) of pure product. M.p. 212-214°C. 1 H NMR (CDCI3, 700 MHz), δ ppm: 0.89 (t,J = 7.0 Hz, 6H, 2xCH3); 1 .28-1.35 (m, 8H, 4xCH2); 1 ,36-1 ,39 (m, 4H, 2xCH2); 1 ,41- 1 ,45 (m, 4H, 2xCH2); 1 ,51-1 ,55 (m, 4H, 2xCH2); 1 ,87-1 ,91 (m, 4H, 2xCH2); 2.82 (s, 6H, 2x CH3); 4.41 (t,J = 7.0 Hz, 4 H, 2xCH2); 7.46 (s, 2 H, 2xCHAr); 7.62 (s, 2 H, 2xCHAr); 7.80 (dd, J = 5.0 Hz, J = 1 .5 Hz, 2H, 2*CHAr); 8.10 (s, 2 H, 2xCHAr); 8.82 (d, J = 5.0 Hz, 2H, 2xCHAr); 8.90 (s, 2 H, 2xCHAr).
The solubility is too low for 3C NMR. IR-ATR, cm"1: 2928, 2861 , 1708, 1605, 1592, 1406, 1383, 1368, 1239, 1222, 1176, 1 151 , 1 1 17, 1091 , 1043, 988, 923, 863, 832, 808, 796, 701.
Example 2:
Ligand 2 according to the invention is prepared by a one-step synthesis.
Octyl 6,6'-((1 , 1')-[3,3,-bipyridine]-4,4,-diylbis(ethene-2,1-diyl))bis(2- methylbenzo[1 ,2-jb:4,5-0'3difuran-3,7-dicarboxylate) (2)
((3,7-Bis(alkoxycarbony[)-6-methylbenzo[1 ,2-ib:4,5-0]difurano-2- yl)methyl)triphenyl-phosphonium bromide (4.2042 g, 5 mmol) and lithium hydroxide monohydrate (0.4830 g, 11 .5 mmol) were placed in a 100 mL one-necked flask, equipped with a reflux condenser and a magnetic stirrer under nitrogen atmosphere in dry isopropanol (20 mL) and stirred for 5 minutes. [2,2'-Bipyridine]-4,4'- dikarboaldehyd (0.5088 g, 2.4 mmol) was added and the temperature was raised to 60°C for 5 minutes. The mixture was stirred at this temperature for 40 minutes, water (45 mL) added, filtered the resulting precipitate, which was washed with water (3x30 mL) and methanol (3 x 25 mL) and air dried to give 2.80 g of a dark orange powder. The crude product was heated in boiling p-xyiene (20 mL) containing a crystal of iodine for 1.5 hours. A part of the p-xylene (17 mL) was distilled off and methanol (40 mL) was added to the residue and stirred at reflux for 30 minutes to solidify the product. It was allowed to cool to room temperature and stirred overnight. The precipitate was filtered off, washed with methanol (2x 15 ml) and air dried to give 2.50 g (92%) of an orange product. M.p. 126-128°C. H NMR (CDCl3, 400 MHz), δ ppm: 0.85-0.95 (m, 12H, 4xCH3); 1 ,24-1 ,48 (m, 32H, 16xCH2); 1 ,50-1 ,62 (m, 8 H, 4xCH2); 1 ,86-1 ,98 (m, 8 H, 4xCH2); 2.82 (s, 6H, 2xCH3); 4.41 (t, J = 6.9 Hz, 4 H,
2xCH2); 4.47 (t, J = 6.9 Hz, 4 H, 2*CH2); 7.51 (dd, J = 5.2 Hz, J = 1.2 Hz, 2H, 2xCHAr); 7.60 (d, J = 16.2 Hz, 2H, 2xCHAr); 7.99 <d, J = 3.7 Hz, 4H, 4xCHAr); 8.17 (d, J = 16.2 Hz, 2H, 2xCHAr); 8.58 (s, 2 H, 2xCHAr); 8.72 (d, J = 5.0 Hz, 2H, 2*CHAr). 13 C NMR (CDCI3, 100 MHz), δ ppm: 14.11 (4 x CH3); 14.68 (2xCH3); 22.67 (4xCH2); 26.15 (2xCH2); 26.28 (2xCH2); 28.80 (4xCH2); 29.26 (2xCH2); 29.27 (2xCH2); 29.30 (2*CH2); 29,36 (CH2); 31.83 (4xCH2); 64.58 (2xCH2); 64.97 (2xCH2); 102.69 (2xCH); 103.17 (2xCH); 109.09 (2xC); 110.72 {2*C); 119.23 (2xCH); 119.38 (2xCH); 120.68 (2xCH); 123.83 (2xC); ); 125.50 (2xC); 132.12 (2xCH); 144.07 (2xC); 149.16 (2xCH); 151.09 (2xC); 151.44 (2xC); 155.75 (2xC); 158.73 (2xC); 163.59 (2*0); 164.03 (2xC); 164.98 (2xC). IR-ATR cm"1 : 2923, 2854, 1705, 1605, 1588, 1554, 1401 , 1362, 1347, 1259, 1187, 150, 1082, 1052, 969, 960, 854, 820, 782, 704.
Example 3:
Ligand 3 of the invention is prepared by a one-step synthesis.
((3, 7-Bis{alkoxycarbonyl)-6-methylbenzo[1 ,2-6:4,5-6 ]difurano-2-yl)methyl)- triphenylphosphonium bromide (5.0450 g, 6 mmol) and lithium hydroxide hydrate (0.5880 g, 14 mmol) were placed in a 100 ml_ one-necked flask under nitrogen atmosphere in dry isopropanol (24 mL) and stirred for 5 minutes. 5H-cyc!openta[1 ,2- 0:5,4-6]dipyridin-5-one (1 .0920 g, 6 mmol) was added and the temperature was raised to 60°C for 15 minutes. The mixture was stirred at this temperature for 20 minutes. Water (20 mL), chloroform (100 mL) and brine (20 mL) were added and the layers were separated. The aqueous layer was extracted with chloroform (2x100 mL) and the combined chloroform layers were washed with brine and dried with anhydrous magnesium sulfate. The solvent was removed and the crude product was purified by flash chromatography on silica gel, eluted with methanol:dich!oromethane in ratio 98:2, yielding 2.11 g (53%), a pale orange crystalline solid. M.p. 84-86°C. 1 H NMR (CDCI3, 400 MHz), δ ppm: 0,85-0,90 (m, 6H, 2xCH3); 1 ,25-1 ,46 (m, 16 H, 8xCH2); 1 ,49-1 ,59 (m, 4H, 2xCH2); 1 ,83-1 ,96 (m, 4H, 2xCH2); 2.82 (s, 3H, CH3); 4.41 (t, J = 6.79 Hz, 2H, CH2); 4.48 (t, J = 6.7 Hz, 2H, CH2); 7.33 (dd, J = 8.0 Hz, J = 4.8 Hz, 1 H, CHAr); 7.42 (dd, J = 8.0 Hz, J = 4.8 Hz, 1 H, CHAr); 8.05 (d, J = 0.4 Hz, 1 H, CHAr); 8.15 (dd, J = 8.0 Hz, J = 1.2 Hz, 1 H, CHAr); 8.17 (s, H, CHAr); 8.43 (s, H, CHAr); 8.74 (dd, J = 4.8 Hz, J = 1.2 Hz, 1 H, CHAr); 8.76 (dd, J = 4.8 Hz, J = 1.2 Hz, 1 H, CHAr); 9.12 (dd, J = 8.0 Hz, J = 1.2 Hz, 1 H, CHAr). 3C NMR (CDCI3, 100 MHz), δ
ppm: 14.07 (2 x CH3); 14.93 (CH3); 22.64 (2><CH2); 26.19 (2xCH2); 28.75 (CH2); 28.79 (CH2); 29.21 (CH2); 29.23 (CH2); 29.31 (2xCH2); 31.81 (2xCH2); 64.72 (CH2); 65.35 (CH2); 102.67 (CH); 103.75 (CH); 109.09 (C); 113.82 <CH); 114.15 (C); 122.98 (2*CH); 123.23 (C); 127.01 (C); 127.92 (CH); 130.15 (C); 132.97 (C); 133.99 (CH); 134.51 (C); 150.56 (CH); 150.68 (CH); 151.39 (C); 151.73 (C); 156.45 (C); 156.87 (C); 158.74 (C); 163.33 (C); 163.85 (C); 165.52 (C).). IR-ATR, cm"1: 2922, 2853, 1705, 1416, 1395, 1348, 1262, 1243, 1 192, 1147, 1089, 1056, 963, 894, 855, 813, 806, 781 , 745, 724, 705.
Example 4:
Complex 4 according to the invention is prepared by a one-step synthesis.
Mixture of dichioro(p-cymene)ruthenium (II) dimer (0.3062 g, 0.5 mmol) and octyl 6,6'-([2,2'-bipyridine]-4,4'-diyl)bis(2-methylbenzo [ ,2-0:4,5-0]difuran-3- carboxylate) (0.8090 g, 1 mmol) in dry W,W-dimethylformamide (40 ml_) was heated in the dark at 150°C for 2 hours, monitoring the disappearance of substrate using a UV- Vis spectrometry. 2,2'-Bipyridine-4,4'-dicarboxylic acid (0.2442 g, 1 mmol) was added and stirred at 150°C for a further 4 hours. Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for another 4 hours. It was cooled to room temperature, the precipitate was filtered off and W,W-dimethylformamide removed using a rotary evaporator. To the residue water (100 mL) was added and the precipitate filtered. The precipitate was washed with more water (100 mL) and dried to give 0.985 g of crude product. The product was purified twice on Sephadex LH-20, eluted with W,W-dimethylformamide and the main band collected to yield 0.440 g (35%) of black, glossy product. The total product was taken up in ethanol and titrated with 0.5 M aqueous solution of tetrabutylammonium hydroxide up to pH = 9. The mixture was stirred for 5 minutes, filtered, acidified with 0.01 M HN03 to pH = 5.2 and the solvents were removed. The resulting precipitate was washed with water at pH 5.2 and dried to give the tetrabutylammonium salt as a black powder, M.p 300°C. Due to the complex mixture of diastereomeric products NMR spectra were unreadable. IR-ATR, cm"1: 2962, 2935, 2856, 2100, 1707, 161 1 , 1467, 1426, 1402, 1362, 1305, 1235, 1 176, 1083, 1019, 979, 921 , 853, 807, 782, 705, 473.
Example 5:
The complex 5 of the present invention is prepared by a one-step synthesis.
Mixture of dichloro(p-cymene)ruthenium(ll) dimer (0.3062 g, 0.5 mmol) and 6,6l-([2,2,-bipyridine]-4,4'-diy[)bis(2-methylbenzo[1 ,2-0:4,5-0]d!furan-3-carboxy^ acid) (1.1691 g, 2 mmoi) in dry Λ/,/V-dimethyiformamide (40 mL) was heated in the dark, at a temperature of 150°C for 4 hours, monitoring the disappearance of substrate using a UV-Vis spectrometry. Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for another 4 hours. It was cooled to room temperature, the precipitate was filtered off and /V,/V-dimethylformamide removed using a rotary evaporator. Water (100 mL) was added to the residue and the precipitate was filtered. The precipitate was washed with more water (100 mL) and dried to give 0.985 g of crude product. The product was purified twice on Sephadex LH-20, eluted with Λ/,/V-dimethylformamide and the main band collected to yield 0.775 g (56%) of black, glossy product. The total product was taken up in ethanol and titrated with 0.5 M aqueous solution of tetrabuty!ammonium hydroxide up to pH = 9. The mixture was stirred for 5 minutes, filtered, acidified with 0.01 M HNO3 to pH = 5.2 and the solvents were removed. The resulting precipitate was washed with water at pH 5.2 and dried to give the tetrabutylammonium salt as a black powder, M.p.> 300°C. Due to the complex mixture of diastereomeric products NMR spectra were unreadable. IR-ATR, cm"1 : 2962, 2935, 2103, 1707, 1611 , 1426, 1402, 1362, 1236, 1176, 1083, 1017, 980, 922, 854, 809, 705, 473.
Example 6:
Complex 6 according to the invention is prepared by a one-step synthesis.
Mixture of dimer of dichloro(p-cymene)ruthenium (II) (0.3062 g, 0.5 mmol) and octyi 6,6'-((1 ,rH3l3'-bipyridine]-4,4,-diytbis(eteno-2, 1-diyl))bis(2- methylbenzo[1 ,2-b:4,5-6']difuran-3,7-dicarboxylate) (1.1734 g, 1 mmol) in dry N,N- dimethylformamide (40 mL) was heated in the dark at 150°C for 2 hours, monitoring the disappearance of substrate using a UV-Vis spectrometry. 2,2'-Bipyridine-4,4'- dicarboxylic acid (0.2442 g, 1 mmol) was added and stirred at 150°C for 4 hours. Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for a further 4 hours. Mixture was cooled to room temperature, the precipitate was filtered off and N,W-dimethylformamide removed using a rotary evaporator. Water (100 mL) was added to the residue and the precipitate filtered. The precipitate was washed with more water (100 mL) and dried to give 1 .182 g of crude product. The product was
purified twice on Sephadex LH-20, eluted with /V-dimethylformamide and the main band collected to yield 0.834 g (51%) of b!ack, glossy product. The total product was taken up in ethanoi and titrated with 0.5 M aqueous solution of tetrabutyiammonium hydroxide up to pH = 9. The mixture was stirred for 5 minutes, filtered, acidified with 0.01 M HN03 to pH = 5.2 and the solvents were removed. The resulting precipitate was washed with water at pH 5.2 and dried to give the tetrabutyiammonium salt as a black powder, M.p.> 300°C. Due to the complex mixture of diastereomeric products NMR spectra were unreadable. IR-ATR, cm"1: 2960, 2923, 2853, 2097, 1705, 1601 , 1360, 1246, 1181 , 1057, 960, 861 , 781 , 473.
Example 7:
Complex 7 according to the invention is prepared by a one-step synthesis.
Mixture of dimer of dichloro(p-cymene)ruthenium (II) (0.3062 g, 0.5 mmoi) and 6,6'-((1 ,1 ,H3,3,-bipyridine]-4,4,-diy[bis(eteno-2,1-diyl))bis(2-methylbenzo[1 J2- 6:4,5-jf>']difuran-3,7-dicarboxy!ic) acid (1.4492 g, 2 mmol) in dry N,N- dimethylformamide (40 ml_) was heated in the dark at 150°C for 4 hours, monitoring the disappearance of substrate using a UV-Vis spectrometry. Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for another 4 hours. The mixture was cooled to room temperature, the precipitate was filtered off and N,N- dimethylformamide removed using a rotary evaporator. Water (100 mL) was added to the residue and the precipitate filtered off. The precipitate was washed with more water (100 mL) and dried to give 1.305 g of crude product. The product was purified twice on Sephadex LH-20, eluted with Λ/,Ν-dimethylformamide and the main band collected, yielding 0.9150 g (59%) of black, glossy product. The total product was taken up in ethanoi and titrated with 0.5 M aqueous solution of tetrabutyiammonium hydroxide up to pH = 9. The mixture was stirred for 5 minutes, filtered, acidified with 0.01 M HNO3 to pH = 5.2 and the solvents were removed. The resulting precipitate was washed with water at pH 5.2 and dried to give the product as a black powder, M.p.> 300°C. Due to the complex mixture of diastereomeric products NMR spectra were unreadable. IR-ATR, cm"1: 2960, 2922, 2099, 1972, 1694, 1599, 1419, 1362, 1243, 1 172, 1046, 954, 861 , 81 1 , 722.
Example 8:
Complex 8 according to the invention is prepared by a one-step synthesis.
Dinner dichloro(p-cymene)ruihenium (il) (0.1531 g, 0.25 mmol) and ester octyl ester 2-((5H-cyclopenta[ ,2~0:5,4"i ']dipirydyn-5-ylidene)methyl)-6-methyibenzo[1 ,2- 0:4,5-0']difuran-3,7-dicarboxylic (0.3314 g, 0.5 mmol) in dry /V,A/-dimethylformamide (20 mL) was heated in the dark at 150°C for 2 hours, monitoring the disappearance of substrate using a UV-Vis spectrometry. Was added 2,2'-bipyridine-414'-dicarboxy]ic acid (0.1221 g, 0.5 mmol) and stirred at 150°C for 4 hours. Was added ammonium thiocyanate (2.74 g, 36.5 mmol) and stirred at 150°C for a further 4 hours. Coo! to room temperature, the precipitate was filtered off and remove N,/V-dimethyIformamide on a rotary evaporator. To the residue was added water (50 mL) and filter the precipitate. The precipitate was washed with more water (50 mL) and dried to give 0.311 g of a crude brown product. The product was purified twice on Sephadex LH- 20, eiuted with N,/V-dimethylformamide and the main band collected to yield 0.206 g (37%) of black, glossy product. The total product was taken up in ethanol and titrated with 0.5 M aqueous solution of tetrabutylammonium hydroxide up to pH = 9.
The mixture was stirred for 5 minutes, filtered, acidified with 0.01 HN03 to pH = 5.2 and the solvents were removed. The resulting precipitate was washed with water at pH 5.2 and dried to give the tetrabutylammonium salt as a black powder, mp> 300°C. Due to the complex mixture of diastereomeric products N R spectra were unreadable. IR-ATR cm"1 : 2960, 2939, 2859, 2102, 1970, 1708, 1601 , 1404, 1364, 1244, 190, 1064, 958, 866, 810, 782, 749, 702, 676, 473.
Example 9:
Complex 9 according to the invention is prepared by a one-step synthesis.
The mixture of dimer of dichloro(p-cymene)ruthenium (II) (0.3062 g, 0.5 mmol) and 2-((5H-cyclopenta[1 ,2- :5,4-b']dipirydyn-5-yiidene)methyl)-6- methylbenzo[1 ,2-0:4,5-0']difuran-3,7-dicarboxy!ic acid (0.8768 g, 2 mmol) in dry N,N- dimethylformamide (40 mL) were heated in the dark at 150DC for 4 hours, monitoring the disappearance of substrate using a UV-Vis spectrometry. Ammonium thiocyanate (2.74 g, 36.5 mmol) was added and stirred at 150°C for a further 4 hours. The mixture was cooled to room temperature, the precipitate was filtered off and N,N- dimethylformamide removed using a rotary evaporator. Water (100 mL) was added to the residue and the precipitate filtered. The precipitate was washed with more water (100 mL) and dried to give 0.872 g of crude product. The product was purified twice
on Sephadex LH-20, eluted with Λ/,/V-dimethyl-formamide and the main band collected, yielding 0.6237 g (57%) of black, glossy product. The total product was taken up in ethanol and titrated with 0.5 M aqueous solution of tetrabutylammonium hydroxide up to pH = 9. The mixture was stirred for 5 minutes, filtered, acidified with 0.01 M HN03 to pH = 5.2 and the solvents were removed. The resulting precipitate was washed with water at pH 5.2 and dried to give the product as a black powder, M.p.> 300°C. Due to the complex mixture of diastereomeric products NMR spectra were unreadable. IR-ATR cm"1: 2962, 2932, 2877, 2107, 1969, 1700, 1603, 1413, 1362, 1183, 1049, 954, 868, 809, 756, 644, 568, 455.
Claims
1. A ligand for synthesis of the photosensitizing ruthenium complexes use, wherein said ligand is at least one selected from the group comprising: compound of formula I
(Formula I)
wherein
Ri = H, alkyl, alkene, alkyne, aromatic hydrocarbon, polyglycol, organic salt, preferably tetrabutylammonium, and inorganic, preferably sodium; compound of formuia II
(Formula II)
wherein R-i = H, alkyl, alkene, alkyne, aromatic hydrocarbon, polyglycol, organic salt, preferably tetrabutylammonium, and inorganic, preferably sodium;
2. Symmetrica! or asymmetrical photosensitizing ruthenium complex for use in DSSC wherein said complex is selected from the group comprising:
complex of formula IV,
wherein Li = the ligand of formula I, L2 = a !igand of formula V;
complex of formula IV, wherein L-i ~ ligand of formula II, L2 = ligand of formula
V;
complex of formula IV, wherein U = L2 = ligand of formula I I;
complex of formula IV, wherein L-j = ligand of formula III, L2 = ligand of formula V;
complex of formula IV, wherein Li = L2 = ligand of formula III.
3. A method for the preparing a ligand 6,6'-([2,2'-bipyridine]-4,4'-diyl)bis(2- methylbenzo[1 ,2-b: 4,5-j ']difuran-3-carboxylic acid) (1 ) of Formula I, as well as esters and salts thereof, wherein said method comprises the step of obtaining the ligand 1 by carrying out a Sonogashira reaction of 4,41-diha[ogeno-2,2'-bipyridine with ethynyltrimethylsilane in a solvent with a palladium catalyst, with or without addition of a phosphine, in the presence of copper halide and amine as a base, removing the trimethylsilyl groups from the intermediate product without isolation thereof by fluoride or alkaline hydrolysis in a mixture of water and alcohol or tetrahydrofuran, reacting 4,4-diethynyi-2 2'-bipyridine without isolation thereof with 5-hydroxy-6-haio-2-methyt- benzofuran-3-carboxylate at room or higher temperature to yield the ligand of formula I, and if necessary, hydrolyzing said ligand under basic or acidic conditions and isolating the product.
4. The method according to claim 3, wherein the solvent is selected from aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably the solvent is selected from toluene, xylene, tetrahydrofuran, dimethyl sulfoxide, acetonitrile nad 1 ,4-dioxane.
5. The method according to claim 3, wherein the catalyst is a palladium compound selected from the group consisting of palladium(!l) dihalides, pa!ladium(li) acetate, palladium(ll) sulfate, bis(triphenylphosphine)palIadium(ll) dichloride, bis(tricyclopentylphosphine) palladium(ll) dichloride, bis(tricyciohexylphosphine) paliadium(ll), bis(dibenzylideneacetone)palladium(0), tetrakis (triphenylphosphine) pailadium(O), preferably [1 ,1'-bis(diphenylphosphino)ferrocene]dichioropalladium(ll).
6. The method according to claim 3, wherein the reaction is carried out with or without addition of an aromatic or nonaromatic phosphine.
7. The method according to claim 3, wherein the reaction is carried out with the addition of a copper halide, preferably copper iodide.
8. A method according to claim 3, wherein the reaction is carried out in the presence of aliphatic, alicyclic, aromatic, heterocyclic amine, preferably diisopropylamine, at room temperature or higher temperature.
9. The method according to claim 3, wherein the trimethylsilyl groups in the intermediate product are removed without isolation thereof using organic or inorganic
fluorides or alkaline hydrolysis in a mixture of water and alcohol or tetrahydrofuran, preferaiby the trimethylsily! groups in the intermediate product are removed with tetrabutyiammonium fluoride.
10. The method according to claim 3, wherein the obtained 4,4-diethynyi-2,2'- bipyridine, without isolation thereof, is reacted with an ester of 5-hydroxy-6-halo-2- methyl-benzofuran-3-carboxylic acid in the same flask, preferably the obtained 4,4- diethynyl-2,2'-bipyridine is reacted with an ester of 5-hydroxy-6-0romo-2-methyl- benzofuran-3-carboxylic acid or 5-hydroxy-6-iodo-2-methy!-benzofuran-3-carboxylic acid, especially with an ester of 5-hydroxy-6-iodo-2-methyl-benzofuran-3-carboxy[ic acid.
11. The method according to claim 3, wherein the reaction of 4,4'-diethynyi- 2,2'-bipyridine with ester of 5-hydroxy-6-iodo-2-methyl-benzofuran-3-carboxylic acid is carried out at room temperature or higher temperature, preferably at a temperature of 80°C.
12. A method for the preparing a ligand 6,6'-((1 ,1 'H3,3'-b!pyridine]-4,4'- diylbis(eteno-2,1-diyl))bis(2-methylbenzo[1 ,2-6:4, 5-6']difuran-3,7-dicarboxylic) acid (2) of Formula II, and esters and salts thereof, wherein the method comprises step of carrying out the Wittig reaction of [2,2'-bipyridine]-4,4'-dikarboaldehyde with ((3,7- bisfalkoxycarbonylJ-e-methylbenzotl ^-jb^.S-bldifuran^-ylJmethy tritriphenyl- phosphonium haiide in an organic solvent in the presence of a base at room or higher temperature to yield the ligand of formula i, and if necessary, hydrolyzing said ligand under basic or acidic conditions and isolating the product.
13. The method according to claim 12, wherein the solvent is selected from the group of an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N- substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably isopropanol.
14. The method according to claim 12, wherein the base is alkali metal hydroxide or mixture thereof, preferably lithium hydroxide or a hydrate thereof.
15. The method according to claim 12, wherein the reaction is carried out at room temperature or higher temperature, preferably at the reflux temperature of isopropanol.
16. A method for the preparing a ligand 2-((5/-/-cyclopenta[1 , 2-0:5,4- ^dipirydyn-S-ylideneJmethylJ-B-methylbenzofl ,2-i>:4,5-£>']difuran-3,7-dicarboxylic acid (3) represented by formula Hi and esters and salts thereof, wherein said method comprises carrying out the Wittig reaction of 5/-/-cyc!openta[1 ,2-£>: 5,4-i>1dipyridin-5- one with ((3,7-bis(alkoxycarbonyl)-6-methylbenzo[ ,2-6:4,5-01difuran-2-yl)methyl) tritriphenyiphosphonium halide in a solvent, in the presence of a base at room or higher temperature to yield the ligand of formula i, and if necessary, hydrolyzing said iigand under basic or acidic conditions and isolating the product.
17. The method according to claim 16, wherein the solvent is selected from the group of an alcohol, hydrocarbon, aliphatic, cycloaiiphatic or aromatic hydrocarbon, aiiphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N- substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably isopropanoi.
18. The method according to claim 16, wherein the base is alkali metai hydroxide or mixture thereof, preferably used lithium hydroxide or a hydrate thereof.
9. The method according to claim 16, wherein the reaction is carried out at room temperature or higher temperature, preferably at the reflux temperature of isopropanoi.
20. A method for the preparing of c/s-bis{isothiocyanate)(6,6'-([2,2'- bipyridine]-4,4'-diyl)b!s(2-methylbenzo[1 ,2-i):4,5-0']difuran-3-karboksylo))(2,2'- bipyridyl-4,4'-dikarboksylo)ruthenium(II) complex (4) of formula IV, wherein L-i = the ligand of formula I, L2 = a ligand of formula V, and esters and salts thereof, wherein the method for obtaining of complex 4 comprises reacting ruthenium(ll!) chloride or dimer of dichloro(p-cymeno)ruthenium(ll) with ligand 1 , 2,2'-bipyridine-4,4'- dicarboxylic acid and inorganic thiocyanate in a solvent and isolating the product.
21 . The method according to claim 20, wherein the source of ruthenium is preferably a dimer of dichloro(p-cymene)ruthenium(ll).
22. The method according to claim 20, wherein the solvent is selected from the group of alcohol, hydrocarbon, aliphatic, cycloaiiphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N-substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably W,W-dimethylformamide.
23. The method according to claim 20, wherein the complex 4 is obtained in one process, without isolation of intermediates.
24. The method according to claim 20, wherein the reaction is carried out at room temperature or higher temperature, preferably at a temperature of 140-150°C.
25. A method for the preparing of c/s-bisiisothiocyanatejbisfe.e'-ip^'" bipyhdine]-4,4'-diyl)bis(2-methylbenzo[1 ,2-0:4,5-jb']difuran-3-karboksylo))ruthenium(il) complex (5) the formula IV, wherein l_i = L2 = a Iigand of formula i, as well as esters and salts thereof, wherein the method for obtaining the complex 5 comprises reacting ruthenium chloride (111) or dimer dichloro(p-cymene)ruthenium(ll) with Iigand 1 and inorganic thiocyanate in a solvent and isolating the product.
26. The method according to claim 25, wherein the source of ruthenium is preferably a dimer dichloro(p-cymene)ruthenium(ll).
27. The method according to claim 25, wherein the solvent is selected from the group of an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N- substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably A/,A/-dimethylformamide.
28. The method according to claim 25, wherein the complex 5 is obtained in one process, without isolation of intermediates.
29. The method according to claim 25, wherein the reaction is carried out at room temperature or higher temperature, preferably at a temperature of 140-150°C.
30. A method for the preparing of c/s-bis{isothiocyanate)(6,6'-((1 ,1 ')-[3,3'- bipyridine]-4,4,-diylbis(eteno-2,1 -diyl))bis(2-methylbenzo[1 ,2-b:4,5-ji)']difuran-3,7- dikarboksyio))(2,2'-bipyridyl-4,4'-dikarboksylo)ruthenium(!l) complex (6) of formula IV, wherein l_i = Iigand of formula II, L2 = Iigand of formula V, and esters and salts thereof, wherein the method for obtaining a complex 6 comprises reacting ruthenium(lll) chloride or dichloro(p-cymeno)ruthenium(ll) dimer with Iigand 2, 2,2'- bipyridine-4,4'-dicarboxylic acid and inorganic thiocyanate in a solvent and isolating the product.
31. The method according to claim 30, wherein the source of ruthenium is preferably dichloro(p-cymene)ruthenium(ll) dimer.
32. The method according to claim 30, wherein the solvent is selected from the group of an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N- substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably Λ/,Ν-dimethylformamide.
33. The method according to claim 30, wherein the complex 6 is prepared in one method without isolation of intermediates.
34. The method according to claim 30, wherein the reaction is carried out at room temperature or higher temperature, preferably at a temperature of 140-150°C.
35. A method for the preparing of c/s-bisiisothiocyanateJbisiG.G'-ifl ')-^^'- bipyridine]-4,4,-diylbis(eteno-2,1 -diyl))bis(2-methylbenzo[1 ,2-i):4,5- ),]difuran-3,7- dikarboksy!o)ruthenium(ll) complex (7), of formula IV, wherein l_i = l_2 = ligand of formula II and esters and salts thereof, wherein the complex 7 is obtained by reacting ruthenium chloride (111) or dichloro(p-cymene)ruthenium (II) dimer with ligand 2, and inorganic thiocyanate in a solvent and isolating the product.
36. The method according to claim 35, wherein the source of ruthenium is preferably dichloro(p-cymene)ruthenium(ll) dimer.
37. The method according to claim 35, wherein the solvent is selected from the group of an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N- substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably W,/V-dimethylformamide.
38. The method according to claim 35, wherein the complex 7 is obtained in one process, without isolation of intermediates.
39. The method according to claim 35, wherein the reaction is carried out at room temperature or higher temperature, preferably at a temperature of 140-150°C.
40. A method for the preparing of c/s-bis(isothiocyanate)(2-((5H- cyclopentatl ^-b!S^-^Jdipirydyn-S-ylideneimethylJ-e-methy!benzon ^-/)^^- £)']difuran-3,7-dikarboksy!o){2,2'-bipyridyl-4,4'-dikarboksylo)ruthenium(ll) complex (8), of formula IV, wherein l_i = ligand of formula Ml, L2 = ligand of formula V; and esters and salts thereof, wherein the method for obtaining complex 8 comrpises reacting ruthenium chloride (III) or dichloro(p-cymene)ruthentum (li) dimer with ligand 3, 2,2'-
bipyridine-4,4'-dicarboxylic acid and an inorganic thiocyanate in a solvent and isolating the product.
41. The method according to claim 40, wherein the source of ruthenium is preferably dichloro(p-cymene)ruthenium(ll) dimer.
42. The method according to claim 40, wherein the solvent is selected from the group of an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N- substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably A/./ -dimethylformamide.
43. The method according to claim 40, wherein complex 8 is obtainable in one process, without isolation of intermediates.
44. The method according to claim 40, wherein the reaction is carried out at room temperature or higher temperature, preferably at a temperature of 140-150°C.
45. A method for the preparing of c s-bis(isothiocyanate)bis(2-((5H- cyc!openta[1 , 2-0:5, 4-/)'3dipirydyn-5-ylidene)methyl)-6-methylbenzo[1 , 2-^:4,5- 0']difuran-3,7-dikarboksylo)ruthenium(ll) complex (9) of formula IV, wherein Li = L2 = ligand of formula 111, wherein the method for obtaining complex 9 comprises reacting ruthenium chloride (111) or dimer dichloro(p-cymene)ruthenium (II) ligand 3 and thiocyanate inorganic solvent and isolating the product.
46. The method according to claim 45, wherein the source of ruthenium is preferably dichloro(p-cymene)ruthenium(ll) dimer.
47. The method according to claim 45, wherein the solvent is selected from the group of an alcohol, hydrocarbon, aliphatic, cycloaliphatic or aromatic hydrocarbon, aliphatic halohydrocarbon, nitrile, ether, ketone, ester or lactone, N- substituted lactam, amide, cyclic urea, sulfoxide or water or a mixture of these solvents, preferably W,A/-dimethyIfarmamide.
48. The method according to claim 45, wherein the complex 9 is obtained in one process, without isolation of intermediates.
49. The method according to claim 45, wherein the reaction is carried out at room temperature or higher temperature, preferably at a temperature of 140- 50°C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018208712A1 (en) * | 2017-05-09 | 2018-11-15 | Warner Babcock Insitute For Green Chemistry, Llc | Stilbene and fused stilbene derivatives as solar cell dyes |
| WO2020014195A1 (en) * | 2018-07-10 | 2020-01-16 | Ambient Photonics, Inc. | Solar cell dyes for copper redox based dye sensitized solar cells and combinations thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5463057A (en) | 1992-08-21 | 1995-10-31 | Ecole Polytechnique Federale De Lausanne, (Epfl) | Bi-pyridyl-rumetal complexes |
| WO2012017869A1 (en) * | 2010-08-03 | 2012-02-09 | 富士フイルム株式会社 | Metal complex dye, photoelectric conversion element and photoelectrochemical cell |
-
2015
- 2015-01-05 PL PL410875A patent/PL238407B1/en unknown
- 2015-12-23 WO PCT/PL2015/000206 patent/WO2016111636A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5463057A (en) | 1992-08-21 | 1995-10-31 | Ecole Polytechnique Federale De Lausanne, (Epfl) | Bi-pyridyl-rumetal complexes |
| WO2012017869A1 (en) * | 2010-08-03 | 2012-02-09 | 富士フイルム株式会社 | Metal complex dye, photoelectric conversion element and photoelectrochemical cell |
Non-Patent Citations (14)
| Title |
|---|
| C.Y. CHEN; M. GRATZEL ET AL., ACSNANO, vol. 3, 2009, pages 3103 |
| C.Y. CHEN; S.J. WU; C.G. WU; J.G. CHEN; K.-C. HO, ANGEW. CHEM., vol. 118, 2006, pages 5954 |
| DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 2012, TANI, YUKIO ET AL: "Metal complex dye, photoelectric conversion element and photoelectrochemical cell", XP002755869, retrieved from STN Database accession no. 2012:195409 * |
| F. GAO; M. GRATZEL ET AL., J. AM. CHEM. SOC., vol. 130, 2008, pages 10720 |
| J. AM. CHEM. SOC., vol. 130, 2008, pages 10720 |
| J. PHYS. CHEM. C, vol. 113, 2009, pages 1998 |
| M.K. NAZEERUDDIN; M. GRÄTZEL ET AL., JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A: CHEMISTRY, vol. 185, 2007, pages 331 |
| M.S. ZAKEERUDDIN; MK NAZEERUDDIN; M. GRAETZEL ET AL., LANGMUIR, vol. 18, 2002, pages 952 |
| MARIUSZ J. BOSIAK ET AL: "Highly efficient benzodifuran based ruthenium sensitizers for thin-film dye-sensitized solar cells", DYES AND PIGMENTS., vol. 121, 19 March 2015 (2015-03-19), GB, pages 79 - 87, XP055260140, ISSN: 0143-7208, DOI: 10.1016/j.dyepig.2015.05.013 * |
| P. GAO; M. GRATZEL ET AL., CHEM. COMMUN., 2008, pages 2635 |
| P. WANG; C. KLEIN; R. HUMPHRY; BAKER, S.M. ZAKEERUDDIN; M. GRATZE, J. AM. CHEM. SOC., vol. 127, 2005, pages 808 |
| P. WANG; S.M. ZAKEERUDDIN; M.K. NAZEERUDDIN; M. GRÄTZEL ET AL., NAT. MATER, vol. 20, 2003, pages 402 |
| Q. YU; P., WANG ET AL., J. PHYS. CHEM. C, vol. 113, 2009, pages 14559 |
| Y. CAO; P. WANG ET AL., J. PHYS. CHEM. C., vol. 113, 2009, pages 6290 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018208712A1 (en) * | 2017-05-09 | 2018-11-15 | Warner Babcock Insitute For Green Chemistry, Llc | Stilbene and fused stilbene derivatives as solar cell dyes |
| US11664171B2 (en) | 2017-05-09 | 2023-05-30 | Ambient Photonics, Inc. | Stilbene and fused stilbene derivatives as solar cell dyes |
| WO2020014195A1 (en) * | 2018-07-10 | 2020-01-16 | Ambient Photonics, Inc. | Solar cell dyes for copper redox based dye sensitized solar cells and combinations thereof |
| US11286244B2 (en) | 2018-07-10 | 2022-03-29 | Ambient Photonics, Inc. | Solar cell dyes for copper redox based dye sensitized solar cells and combinations thereof |
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