US20020082422A1 - Pyridine derivative and its complex - Google Patents
Pyridine derivative and its complex Download PDFInfo
- Publication number
- US20020082422A1 US20020082422A1 US10/024,378 US2437801A US2002082422A1 US 20020082422 A1 US20020082422 A1 US 20020082422A1 US 2437801 A US2437801 A US 2437801A US 2002082422 A1 US2002082422 A1 US 2002082422A1
- Authority
- US
- United States
- Prior art keywords
- complex
- pyridine
- hydrogen
- inclusive
- carbon number
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000003222 pyridines Chemical class 0.000 title abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 40
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 24
- 230000001235 sensitizing effect Effects 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- -1 pyridine compound Chemical class 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 25
- 239000013078 crystal Substances 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 0 [1*]C1=CC(C2=CC([2*])=CC(C3=CC([3*])=CC(C4=NC=CC([4*])=C4)=N3)=N2)=NC=C1 Chemical compound [1*]C1=CC(C2=CC([2*])=CC(C3=CC([3*])=CC(C4=NC=CC([4*])=C4)=N3)=N2)=NC=C1 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- YOWBQVKUBSRDEP-UHFFFAOYSA-N 4-ethyl-2,6-bis(4-ethylpyridin-2-yl)pyridine Chemical compound CCC1=CC=NC(C=2N=C(C=C(CC)C=2)C=2N=CC=C(CC)C=2)=C1 YOWBQVKUBSRDEP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012327 Ruthenium complex Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- ZCUFUJDBZQPCHX-UHFFFAOYSA-N 4-ethyl-2-(4-ethylpyridin-2-yl)pyridine Chemical compound CCC1=CC=NC(C=2N=CC=C(CC)C=2)=C1 ZCUFUJDBZQPCHX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CAJRBFPGFKNRKJ-UHFFFAOYSA-N CCCCC1=CC=N2C(=C1)C1=N3C(=CC(CCC)=C1)C1=N4C(=CC(C)=C1)C1=N(C=CC(C)=C1)C234(C)C Chemical compound CCCCC1=CC=N2C(=C1)C1=N3C(=CC(CCC)=C1)C1=N4C(=CC(C)=C1)C1=N(C=CC(C)=C1)C234(C)C CAJRBFPGFKNRKJ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011011 black crystal Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RSHBFZCIFFBTEW-UHFFFAOYSA-M tetrabutylazanium;thiocyanate Chemical compound [S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC RSHBFZCIFFBTEW-UHFFFAOYSA-M 0.000 description 2
- VJXRKZJMGVSXPX-UHFFFAOYSA-N 4-ethylpyridine Chemical compound CCC1=CC=NC=C1 VJXRKZJMGVSXPX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- PNIBABOSICIYOY-UHFFFAOYSA-N CCC1=CC(C2=CC(CC)=CC(C3=CC(CC)=CC(C4=NC=CC(CC)=C4)=N3)=N2)=NC=C1.CCC1=CC=NC=C1 Chemical compound CCC1=CC(C2=CC(CC)=CC(C3=CC(CC)=CC(C4=NC=CC(CC)=C4)=N3)=N2)=NC=C1.CCC1=CC=NC=C1 PNIBABOSICIYOY-UHFFFAOYSA-N 0.000 description 1
- RHJUGVDEAPAEOO-UHFFFAOYSA-N CCC1=CC(C2=CC(CC)=CC(C3=CC(CC)=CC(C4=NC=CC(CC)=C4)=N3)=N2)=NC=C1.O=C(O)C1=CC(C2=CC(C(=O)O)=CC(C3=CC(C(=O)O)=CC(C4=NC=CC(C(=O)O)=C4)=N3)=N2)=NC=C1 Chemical compound CCC1=CC(C2=CC(CC)=CC(C3=CC(CC)=CC(C4=NC=CC(CC)=C4)=N3)=N2)=NC=C1.O=C(O)C1=CC(C2=CC(C(=O)O)=CC(C3=CC(C(=O)O)=CC(C4=NC=CC(C(=O)O)=C4)=N3)=N2)=NC=C1 RHJUGVDEAPAEOO-UHFFFAOYSA-N 0.000 description 1
- SOSPVWJDVNHSLQ-UHFFFAOYSA-N CCN(CC)(CC)OC(=O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)ON(CC)(CC)CC)=C1)C1=N4C(=CC(C(=O)ON(CC)(CC)CC)=C1)C1=N(C=CC(C(=O)ON(CC)(CC)CC)=C1)[Ru]234(N=C=S)N=C=S.COOCC1=CC2=N(C=C1)[Ru]13(N=C=S)(N=C=S)N4=CC=C(C(=O)OC)C=C4C4=N1C(=CC(C(=O)OC)=C4)C1=N3C2=CC(COOC)=C1 Chemical compound CCN(CC)(CC)OC(=O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)ON(CC)(CC)CC)=C1)C1=N4C(=CC(C(=O)ON(CC)(CC)CC)=C1)C1=N(C=CC(C(=O)ON(CC)(CC)CC)=C1)[Ru]234(N=C=S)N=C=S.COOCC1=CC2=N(C=C1)[Ru]13(N=C=S)(N=C=S)N4=CC=C(C(=O)OC)C=C4C4=N1C(=CC(C(=O)OC)=C4)C1=N3C2=CC(COOC)=C1 SOSPVWJDVNHSLQ-UHFFFAOYSA-N 0.000 description 1
- ZMBGMHKIYGEMBR-UHFFFAOYSA-N CCN(CC)(CC)OC(=O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)ON(CC)(CC)CC)=C1)C1=N4C(=CC(C(=O)ON(CC)(CC)CC)=C1)C1=N(C=CC(C(=O)ON(CC)(CC)CC)=C1)[Ru]234(N=C=S)N=C=S.O=C(O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)O)=C1)C1=N4C(=CC(C(=O)O)=C1)C1=N(C=CC(C(=O)O)=C1)[Ru]234(N=C=S)N=C=S Chemical compound CCN(CC)(CC)OC(=O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)ON(CC)(CC)CC)=C1)C1=N4C(=CC(C(=O)ON(CC)(CC)CC)=C1)C1=N(C=CC(C(=O)ON(CC)(CC)CC)=C1)[Ru]234(N=C=S)N=C=S.O=C(O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)O)=C1)C1=N4C(=CC(C(=O)O)=C1)C1=N(C=CC(C(=O)O)=C1)[Ru]234(N=C=S)N=C=S ZMBGMHKIYGEMBR-UHFFFAOYSA-N 0.000 description 1
- GRTCKZZBUGFWAD-UHFFFAOYSA-N COC(=O)C1=CC(C2=CC(C(=O)OC)=CC(C3=CC(C(=O)OC)=CC(C4=NC=CC(C(=O)OC)=C4)=N3)=N2)=NC=C1.COC(=O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)OC)=C1)C1=N4C(=CC(C(=O)OC)=C1)C1=N(C=CC(C(=O)OC)=C1)[Ru]234(N=C=S)N=C=S Chemical compound COC(=O)C1=CC(C2=CC(C(=O)OC)=CC(C3=CC(C(=O)OC)=CC(C4=NC=CC(C(=O)OC)=C4)=N3)=N2)=NC=C1.COC(=O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)OC)=C1)C1=N4C(=CC(C(=O)OC)=C1)C1=N(C=CC(C(=O)OC)=C1)[Ru]234(N=C=S)N=C=S GRTCKZZBUGFWAD-UHFFFAOYSA-N 0.000 description 1
- AFHPTICZSCNNHQ-UHFFFAOYSA-N COC(=O)C1=CC(C2=CC(C(=O)OC)=CC(C3=CC(C(=O)OC)=CC(C4=NC=CC(C(=O)OC)=C4)=N3)=N2)=NC=C1.O=C(O)C1=CC(C2=CC(C(=O)O)=CC(C3=CC(C(=O)O)=CC(C4=NC=CC(C(=O)O)=C4)=N3)=N2)=NC=C1 Chemical compound COC(=O)C1=CC(C2=CC(C(=O)OC)=CC(C3=CC(C(=O)OC)=CC(C4=NC=CC(C(=O)OC)=C4)=N3)=N2)=NC=C1.O=C(O)C1=CC(C2=CC(C(=O)O)=CC(C3=CC(C(=O)O)=CC(C4=NC=CC(C(=O)O)=C4)=N3)=N2)=NC=C1 AFHPTICZSCNNHQ-UHFFFAOYSA-N 0.000 description 1
- 241000394591 Hybanthus Species 0.000 description 1
- RQHZASQXSGTBAY-UHFFFAOYSA-N O=C(O)C1=CC(C2=CC(C(=O)O)=CC(C3=CC(C(=O)O)=CC(C4=NC=CC(C(=O)O)=C4)=N3)=N2)=NC=C1.O=C(O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)O)=C1)C1=N4C(=CC(C(=O)O)=C1)C1=N(C=CC(C(=O)O)=C1)[Ru]234(N=C=S)N=C=S Chemical compound O=C(O)C1=CC(C2=CC(C(=O)O)=CC(C3=CC(C(=O)O)=CC(C4=NC=CC(C(=O)O)=C4)=N3)=N2)=NC=C1.O=C(O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)O)=C1)C1=N4C(=CC(C(=O)O)=C1)C1=N(C=CC(C(=O)O)=C1)[Ru]234(N=C=S)N=C=S RQHZASQXSGTBAY-UHFFFAOYSA-N 0.000 description 1
- KBMCJZAYYNGKKA-UHFFFAOYSA-N O=C(O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)O)=C1)C1=N(C=CC(C(=O)O)=C1)[Ru]23(N=C=S)(N=C=S)N=C=S.O=C(O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)O)=C1)C1=N4C(=CC(C(=O)O)=C1)C1=N(C=CC(C(=O)O)=C1)[Ru]234(N=C=S)N=C=S Chemical compound O=C(O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)O)=C1)C1=N(C=CC(C(=O)O)=C1)[Ru]23(N=C=S)(N=C=S)N=C=S.O=C(O)C1=CC=N2C(=C1)C1=N3C(=CC(C(=O)O)=C1)C1=N4C(=CC(C(=O)O)=C1)C1=N(C=CC(C(=O)O)=C1)[Ru]234(N=C=S)N=C=S KBMCJZAYYNGKKA-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- 244000154870 Viola adunca Species 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- QMHAHUAQAJVBIW-UHFFFAOYSA-N [methyl(sulfamoyl)amino]methane Chemical compound CN(C)S(N)(=O)=O QMHAHUAQAJVBIW-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a pyridine derivative and its ruthenium or osmium complex.
- a dye sensitizing type solar battery which employs a compound having photoelectric exchanging function is described in U.S. Pat. No. 5,463,057.
- Bipyridine and a ruthenium complex of tetrabipyridine are disclosed as examples for compounds having photoelectric exchanging function.
- each of R 1 , R 2 , R 3 , R 4 is independently —OR′, —COOR′, —CONR′, —CHO, —CH 2 OR′, —CN, an alkyl group whose carbon number ranges from 1 to 20 inclusive, or —COONR′ 4 , wherein R′ is a hydrogen, or an alkyl group whose carbon number ranges from 1 to 4 inclusive.
- Another embodiment of the present invention includes a complex of a pyridine compound represented by the following formula (II)
- each of X 1 , X 2 , X 3 , X 4 is independently —OR, —COOR′, —CONR′, —CHO, —CH 2 OR′, —CN, an alkyl group whose carbon number ranges from 1 to 20- inclusive, or —COONR′ 4 , wherein R′ is a hydrogen, or an alkyl group whose carbon number ranges from 1 to 4 inclusive;
- Z is Cl, Br, CN, NCS, or NCO
- M is Ru or Os.
- FIG. 1 is an NMR spectrum of a pyridine derivative according to Example 1;
- FIG. 2 is an IR spectrum of the pyridine derivative according to Example 1;
- FIG. 3 is an NMR spectrum of a complex of a pyridine derivative according to synthetic Examples 3 and 4;
- FIG. 4 is an IR spectrum of the complex of pyridine derivative according to Examples 3 and 4;
- FIG. 5 is an NMR spectrum of a pyridine dimer according to Example 5.
- FIG. 6 is an NMR spectrum of a pyridine dimer according to Example 6.
- FIG. 7 is a UV-VIS absorption spectrum of a complex of a pyridine derivative.
- a complex represented by the following formula (II) and produced from a pyridine derivative tetramer represented by the following formula (I) is superior in absorption peak shift to higher wavelengths which results in effective solar light absorption, when compared to the compounds disclosed in the foregoing U.S. Pat. No. 5,463,057.
- the pyridine derivative in accordance with the present invention is a compound which is represented by the following formula (I)
- each of R 1 , R 2 , R 3 , R 4 is independently selected from —OR′, —COOR′, —CONR′, —CHO, —CH 2 OR′, —CN, an alkyl group whose carbon number ranges from 1 to 20 inclusive, or —COONR′ 4 , where R′ is a hydrogen or an alkyl group whose carbon number ranges from 1 to 4 inclusive.
- the complex of the pyridine derivative of the present invention is a compound which is represented by the following formula (II)
- each of X 1 , X 2 , X 3 , X 4 is independently selected from —OR′, —COOR′, —CONR′, —CHO, —CH 2 OR, —CN, an alkyl group whose carbon number ranges from 1 to 20 inclusive, or —COONR′ 4 , where R′ is a hydrogen or an alkyl group whose carbon number ranges from 1 to 4 inclusive,
- Z is Cl, Br, CN, NCS, or NCO
- M is Ru or Os.
- the alkyl group to be selected for each of R 1 , R 2 , R 3 , R 4 is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl and n-pentyl. Particularly preferable are ethyl and isopropyl.
- the alkyl group whose carbon number ranges from 1 to 4 and which is represented by R′, is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl.
- the pyridine derivative which is represented by formula (I) is preferably a compound in which all R 1 , R 2 , R 3 , R 4 are an ethyl group or an isopropyl group or a compound in which all R 1 , R 2 , R 3 , R 4 are a carboxyl group or its ester.
- Particularly preferable are 4,4 ′, 4′′, 4′′′-tetraethyl-[2,2′;6′,2′′6′′, 2′′′] quaterpyridine, 4,4′,4′′,4′′′-tetraisopropyl [2,2′;6′2′′;6′′2′′′]quarterpyridine, [2,2′;6′,2′′;6′′,2′′′]quaterpyridine-4,4′,4′′,4′′′-tetracarboxylic acid, and [2,2′;6′,2′′; 6′′,2′′′]quaterpyridine-4,4′,4′′,4′′′-tetracarboxylic acid tetra ester.
- the complex of the pyridine derivative which is represented by formula (I) is preferably a compound in which X 1 and X 4 are the same, X 2 and X 3 are the same, all X 1 , X 2 , X 3 , X 4 are a carboxyl group, its ester, or its amid.
- Preferable Z and M are NCS and ruthenium, respectively.
- the compounds in accordance with the present invention can be produced by conventional methods.
- the pyridine derivative of the present invention can be obtained or produced by polymerizing the corresponding pyridine monomer or pyridine dimer.
- a synthetic method starting from a monomer is disclosed in, for example, U.S. Pat. No. 6,463,057 granted to Graetzel et al, J. Am. Chem. Soc., 99, 4947 (1977), and Inorg. Chem., 24, 4573 (1985).
- the yield of the pyridine derivative is poor or very small.
- a large amount of pyridine dimer/trimer derivative is produced as a by-product in addition to the pyridine tetramer derivative.
- well known methods such as distillation or column chromatography have to be used.
- the pyridine derivative of formula (I) is a chelation agent or a (raw material) conductive polymer as well as an intermediate raw material for producing the complex of the pyridine derivative of formula (II).
- the complex of the pyridine derivative of formula (II) has a very high in photoelectric exchanging function or activity and therefore can be used preferably as a coloring material for a dye sensitizing type solar battery.
- a dye sensitizing type solar battery is made of a transparent substrate with a transparent conductive membrane, a conductive substrate opposed to the transparent substrate, and set of sensitizing dye carrying semiconductor electrodes and a catalytic layer which is interposed between the transparent substrate and the conductive substrate. In this solar battery, an electric energy is generated by a photoelectric exchanging function between the transparent membrane and the conductive substrate.
- the sensitizing dye is preferably the complex of the pyridine derivative of formula (II).
- a dye sensitizing type solar battery can be produced by forming an aluminum-doped oxidized titan layer as a semiconductor layer on a conductive substrate.
- An electrode in the form of a layer of a pyridine derivative complex according to the present invention is provided as a dye sensitizer on an outer surface of the oxidized titan layer.
- a transparent electrode which is formed of e.g. a conductive glass, and an electrolyte solution which includes, for example, iodine is filled between the electrodes.
- electrons are found to be localized when compared to a dimer or trimer of a pyridine derivative. This shifts the maximum peak absorption wavelength toward a longer wavelength, a sunlight spectrum (energy) can be converted effectively into electric power.
- the complex of the pyridine derivative of the present invention can be used as a coloring material similar to the conventional or existing coloring materials.
- the resulting reaction solution was added to 2 l of ice water and left standing overnight at a temperature of 5° C. to separate crystals from of the mixture. Thereafter, the crystals were filtrated from the reaction solution. The resulting crystals were well washed with water and were dried in vacuum to obtain a white crystalline compound.
- the reaction solution was cooled down to room temperature, its solvent amount was reduced to about 10 ml, about 100 ml of water were added, and the mixture was left standing overnight at a temperature of 5° C. to separate a crystal.
- the crystal was extracted by filtering, washed with water, and was dried under vacuum to obtain a white crystalline material.
- the resulting crude product was added to a flask under argon, 53 ml of DMF, 701 mg (9.21 mmol)/21 ml of ammonium thiocyanate solution, and 6 ml of triethylamine were added.
- the resulting mixture was stirred for 2 days at a temperature of 110°C.
- About 100 ml of water were added, and the mixture was left to stand overnight at a temperature of 5° C. to separate a crystal.
- the crystal was extracted by filtering, washed with water, and dried under vacuum to obtain a black crystal.
- the crystal was extracted by filtering and was dried under reduced pressure.
- the resulting crude product was refined using a gel column.
- the resulting solution was reduced under pressure reduction, condensed to 10 ml and thereafter, until its pH became 9-10, a 10% solution of tetra-n-butyl-ammonium-hydroxide was added.
- the solution was filtered to remove impurities. Thereafter, the pH of the solution was again adjusted to between 5.20 and 1.50 with nitric acids to obtain compounds which are different in ‘n’ (n: 0-4).
- Example 4-1 To a flask, 2 g of the Example 4-1 and 2 g (4.1 mmol) were added. The resulting mixture was, after being added to 500 ml of DMF, stirred for four hours at a temperature of 140° C. under argon. The mixture was cooled down to 120° C. and was stirred, after addition of 3.1 g (41 mmol)/100 ml of ammonium thiocyanate solution for 2 hours. Then, after cooling the reaction solution down to room temperature, the separated crystal was extracted by filtering, washed with water and dried under vacuum.
- the resulting crude product was melted and refined with a gel column.
- the resulting solution was, under pressure reduction, condensed to about 10 ml and added, until its pH became 9-10, to a 10% solution of tetra-n-butyl ammonium-hydroxide.
- the solution was filtered to remove impurities. Thereafter, the pH of the solution was again adjusted to between 5.20 and 1.50 with nitric acids to obtain a black crystal.
- the ruthenium complex of each of 4,4′-diethyl-[2,2′]bipyridine and, 4,4′,4′′-triethyl-[2,2′;6′,2′′]terpyridine is synthesized in a similar fashion as described in each of Examples 2 to 4.
- the ruthenium complex synthesized from the 4,4′-diethyl-[2,2′]bipyridine is a red crystal
- the ruthenium complex synthesized from the 4,4′,4′′-triethyl-[2,2′;6′,2′′]terpyridine is a green crystal.
- Example 1 With respect to the Example 1, its NMR spectrum and IR spectrum are illustrated in FIG. 1 and FIG. 2, respectively.
- the peak of chemical shift ⁇ 8.46 ppm (411,s) corresponds to 5′-position of hydrogen, 3′′-position of hydrogen, 3′-position of hydrogen, and 5′′-position of hydrogen
- the peak of 3050 cm ⁇ 1 (w) and the peak of 3000-2800 cm ⁇ 1 (m) correspond to the pyridine and —CH 2 CH 3 .
- the present compound can be characterized by NMR spectrum and IR spectrum.
- the present compound can be characterized by mass spectrometry and elemental analysis.
- Example 2 With respect the Example 2, its NMR spectrum and IR spectrum are illustrated in FIG. 3 and FIG. 4, respectively.
- the peak of chemical shift a ⁇ 0.88 ppm (2H,d,J ⁇ 0.9) corresponds to the 3′-position of hydrogen and 5′′-position of hydrogen
- the peak of 3600-2500 cm ⁇ 1 (b), the peak of 3073 cm ⁇ 1 (w), the peak of 3000-2900 cm ⁇ 1 (m), the peak of 2101 cm ⁇ 1 (s), the peak of 171.1 cm ⁇ 1 (m), and the peak of 1605 cm ⁇ 1 (m) corresponds to OH, pyridine skeleton, TBA, NCS, CO, and CO, respectively.
- the present compound can be characterized by NMR spectrum and IR spectrum.
- Example 2 the compound of Example 2 can be characterized by mass spectrometry and elemental analysis.
- FIG. 5 and FIG. 6 illustrate NMR spectrums of the respective derivatives of 4,4′-diethyl-[2,2′]bipyridine and of 4,4′,4′′-triethyl-[2,2′;6′,2′′]terpyridine.
- FIG. 7 shows the complex of ruthenium which is synthesized from each of the carbonic acid derivatives of pyridine dimer, pyridine trimer, and pyridine tetramer.
- the measurement of absorption spectrum was performed such that each compound was dissolved in ethanol.
- the colors of the respective pyridine dimer, pyridine trimer, and pyridine tetramer are red, green, and blue violet.
- FIG. 7 whenever the polymerization degree of pyridine increases, its absorption wavelength shifts to a longer wavelength.
- the complex of the pyridine tetramer derivative may be used as dye sensitizing element which makes it possible to increase photoelectric exchanging performance when compared to a complex of pyridine dimer or trimer derivative as dye sensitizing element.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Pyridine Compounds (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
wherein each of R1, R2, R3, R4 is independently —OR′, —COOR′, —CONR′, —CHO, —CH2OR′, —CN, an alkyl group whose carbon number ranges from 1 to 20 inclusive, or —COONR′4, wherein R′ is a hydrogen, or an alkyl group whose carbon number ranges from 1 to 4 inclusive.
Description
- 1. Field of the Invention
- The present invention relates to a pyridine derivative and its ruthenium or osmium complex.
- A dye sensitizing type solar battery which employs a compound having photoelectric exchanging function is described in U.S. Pat. No. 5,463,057. Bipyridine and a ruthenium complex of tetrabipyridine are disclosed as examples for compounds having photoelectric exchanging function.
- It is an object of the present invention to provide a novel pyridine derivative and its complex.
-
- wherein each of R1, R2, R3, R4 is independently —OR′, —COOR′, —CONR′, —CHO, —CH2OR′, —CN, an alkyl group whose carbon number ranges from 1 to 20 inclusive, or —COONR′4, wherein R′ is a hydrogen, or an alkyl group whose carbon number ranges from 1 to 4 inclusive.
-
- wherein each of X1, X2, X3, X4 is independently —OR, —COOR′, —CONR′, —CHO, —CH2OR′, —CN, an alkyl group whose carbon number ranges from 1 to 20- inclusive, or —COONR′4, wherein R′ is a hydrogen, or an alkyl group whose carbon number ranges from 1 to 4 inclusive;
- wherein Z is Cl, Br, CN, NCS, or NCO; and
- wherein M is Ru or Os.
- The above and other objects, features and advantages of the present invention will be more apparent and more readily appreciated from the following detailed description of preferred exemplary embodiments of the present invention, taken in connection with the accompanying drawings, in which:
- FIG. 1 is an NMR spectrum of a pyridine derivative according to Example 1;
- FIG. 2 is an IR spectrum of the pyridine derivative according to Example 1;
- FIG. 3 is an NMR spectrum of a complex of a pyridine derivative according to synthetic Examples 3 and 4;
- FIG. 4 is an IR spectrum of the complex of pyridine derivative according to Examples 3 and 4;
- FIG. 5 is an NMR spectrum of a pyridine dimer according to Example 5;
- FIG. 6 is an NMR spectrum of a pyridine dimer according to Example 6; and
- FIG. 7 is a UV-VIS absorption spectrum of a complex of a pyridine derivative.
- A complex represented by the following formula (II) and produced from a pyridine derivative tetramer represented by the following formula (I) is superior in absorption peak shift to higher wavelengths which results in effective solar light absorption, when compared to the compounds disclosed in the foregoing U.S. Pat. No. 5,463,057.
- It is to be noted that the existence of the pyridine derivative according to the present invention was not found or suggested due to very, very small yield thereof in the conventional pyridine polymer synthesis. The present inventors were confident of the higher performance of a pyridine tetramer derivative. Thus, they conducted research by employing reaction conditions including a large amount of raw material and longer reaction time. This research resulted in the synthesis of a pyridine tetramer derivative.
-
- in which each of R1, R2, R3, R4 is independently selected from —OR′, —COOR′, —CONR′, —CHO, —CH2OR′, —CN, an alkyl group whose carbon number ranges from 1 to 20 inclusive, or —COONR′4, where R′ is a hydrogen or an alkyl group whose carbon number ranges from 1 to 4 inclusive.
-
- in which each of X1, X2, X3, X4 is independently selected from —OR′, —COOR′, —CONR′, —CHO, —CH2OR, —CN, an alkyl group whose carbon number ranges from 1 to 20 inclusive, or —COONR′4, where R′ is a hydrogen or an alkyl group whose carbon number ranges from 1 to 4 inclusive,
- Z is Cl, Br, CN, NCS, or NCO, and
- M is Ru or Os.
- In formula (I), the alkyl group to be selected for each of R1, R2, R3, R4, is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl and n-pentyl. Particularly preferable are ethyl and isopropyl.
- The alkyl group whose carbon number ranges from 1 to 4 and which is represented by R′, is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl.
- The pyridine derivative which is represented by formula (I) is preferably a compound in which all R1, R2, R3, R4 are an ethyl group or an isopropyl group or a compound in which all R1, R2, R3, R4 are a carboxyl group or its ester.
- Particularly preferable are 4,4 ′, 4″, 4′″-tetraethyl-[2,2′;6′,2″6″, 2′″] quaterpyridine, 4,4′,4″,4′″-tetraisopropyl [2,2′;6′2″;6″2′″]quarterpyridine, [2,2′;6′,2″;6″,2′″]quaterpyridine-4,4′,4″,4′″-tetracarboxylic acid, and [2,2′;6′,2″; 6″,2′″]quaterpyridine-4,4′,4″,4′″-tetracarboxylic acid tetra ester.
- The complex of the pyridine derivative which is represented by formula (I) is preferably a compound in which X1 and X4 are the same, X2 and X3 are the same, all X1, X2, X3, X4 are a carboxyl group, its ester, or its amid. Preferable Z and M are NCS and ruthenium, respectively.
- Particularly preferable are, Ru(2,2′,;6′,2″6′,2′″-quaterpyridine-4,4′,4″,4′″-tetracarboxylic acid tetra methyl ester)(NCS)2, ((C2H5)3NH)4[Ru(2,2′;6′,2″;6″,2′″-quaterpyridine-4,4′,4″,4′″-tetracarboxylate)(NCS)2], ((C4H9)3N)nH4−n[Ru(2,2′;6′,2″;6″,2′″-quaterpyridine-4,4′,4″,4′″-tetracarboxylate)(NCS)2], and Ru(2,2′;6′,2″;6″,2″-quaterpyridine-4,4′,4″,4′″-tetracarboxylic acid)(NCS)2.
- The compounds in accordance with the present invention can be produced by conventional methods.
- The pyridine derivative of the present invention can be obtained or produced by polymerizing the corresponding pyridine monomer or pyridine dimer. A synthetic method starting from a monomer is disclosed in, for example, U.S. Pat. No. 6,463,057 granted to Graetzel et al, J. Am. Chem. Soc., 99, 4947 (1977), and Inorg. Chem., 24, 4573 (1985). However, in this case the yield of the pyridine derivative is poor or very small. In each of these synthesis methods, a large amount of pyridine dimer/trimer derivative is produced as a by-product in addition to the pyridine tetramer derivative. In order to isolate the pyridine tetramer derivative from the mixture of these substances or compounds, well known methods such as distillation or column chromatography have to be used.
- The pyridine derivative of formula (I) is a chelation agent or a (raw material) conductive polymer as well as an intermediate raw material for producing the complex of the pyridine derivative of formula (II).
- The complex of the pyridine derivative of formula (II) has a very high in photoelectric exchanging function or activity and therefore can be used preferably as a coloring material for a dye sensitizing type solar battery. For example, a dye sensitizing type solar battery is made of a transparent substrate with a transparent conductive membrane, a conductive substrate opposed to the transparent substrate, and set of sensitizing dye carrying semiconductor electrodes and a catalytic layer which is interposed between the transparent substrate and the conductive substrate. In this solar battery, an electric energy is generated by a photoelectric exchanging function between the transparent membrane and the conductive substrate. The sensitizing dye is preferably the complex of the pyridine derivative of formula (II). A dye sensitizing type solar battery can be produced by forming an aluminum-doped oxidized titan layer as a semiconductor layer on a conductive substrate. An electrode in the form of a layer of a pyridine derivative complex according to the present invention is provided as a dye sensitizer on an outer surface of the oxidized titan layer. A transparent electrode which is formed of e.g. a conductive glass, and an electrolyte solution which includes, for example, iodine is filled between the electrodes. In the complex of the pyridine derivative of the present invention, electrons are found to be localized when compared to a dimer or trimer of a pyridine derivative. This shifts the maximum peak absorption wavelength toward a longer wavelength, a sunlight spectrum (energy) can be converted effectively into electric power.
- The complex of the pyridine derivative of the present invention can be used as a coloring material similar to the conventional or existing coloring materials.
- Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only, and are not intended to be limiting unless otherwise specified.
- In a flask, 500 ml of 4-ethyl pyridine which is commercially available and 20 g palladium carbon having a palladium content of 5% by weight were mixed. After a four-day reflux while the resulting mixture was stirred, the resulting mixture was filtered to eliminate palladium carbon. The resulting reaction product was distilled under reduced pressure to obtain the above identified quaterpyridine. In this example, 4,4′-diethyl-[2,2′]bypyridine and 4,4′,4″-triethyl-[2,2′;6′,2″]terpyridine were simultaneously produced and separated by the above distillation under reduced pressure.
- In a flask, 3.00 g (7.10 mmol) of the compound of Example 1, 90 ml of sulfuric acid were added and the resulting mixture was stirred until the compound of Example 1 was completely dissolved.
- To the resulting liquid or solution, 16.70 g (56.80 mmol) of 2-potassium chromate were added so that the temperature increased from 30 to 60° C. over the course of six hours. After an overnight reaction, 3 l of the resulting reaction solution were added to an amount of ice water and the resulting mixture was left standing overnight at a temperature of 5°C. to separate crystals from the mixture. Thereafter, the crystals were filtrated from the reaction solution. The resulting crystals were well washed with water and were dried in vacuum. The resulting crude-product and 10 ml of 50% nitric acid were placed in a flask and heated to 60° C. and the resulting mixture was stirred for 5 hours. After stirring, the resulting reaction solution was added to 2 l of ice water and left standing overnight at a temperature of 5° C. to separate crystals from of the mixture. Thereafter, the crystals were filtrated from the reaction solution. The resulting crystals were well washed with water and were dried in vacuum to obtain a white crystalline compound.
- 3.308 (6.79 mmol) of the compound of Example 2 were added to a flask and were refluxed under argon together with 300 ml of dried methanol and 6 ml of sulfuric acid and stirring for 2 days. After lowering the temperature of the solution to room temperature, the reaction solution was added to a solution of saturated sodium hydrogen carbonate. After ethanol elimination from the reaction solution under reduced pressure, a crystal was extracted from the reaction solution by filtering. The resulting crystal was well washed with water and was dried under vacuum to obtain a white crystalline compound.
-
- In a flask, 700 mg (0.921 mmol) of the compound of Example 3-2 were added under argon to 5 mmol of DMF, 700 mg (9.21 mmol)/21 ml of ammonium thiocyanate solution, and 6 ml of triethylamine. The resulting mixture was stirred for 2 days at a temperature of 30° C. After the reaction solution was cooled down to room temperature, its solvent amount was reduced under reduced pressure to about 10 ml. About 100 ml of water were added, and the mixture was left standing overnight at a temperature of 5° C. to separate a crystal. The crystal was extracted by filtering, washed with water, and dried under pressure reduction. The resulting crude product was added to a flask under argon, 53 ml of DMF, 701 mg (9.21 mmol)/21 ml of ammonium thiocyanate solution, and 6 ml of triethylamine were added. The resulting mixture was stirred for 2 days at a temperature of 110°C. After the reaction solution was cooled down to room temperature, its solvent amount was reduced under reduced pressure to about 10 ml. About 100 ml of water were added, and the mixture was left to stand overnight at a temperature of 5° C. to separate a crystal. The crystal was extracted by filtering, washed with water, and dried under vacuum to obtain a black crystal.
- 2.0 mg of the compound of Example 3-3, 2.4 g of tetra-n-butyl-ammonium-thiocyanate, and 30 ml of water were added to a beaker and stirred. The resulting mixture was added, until its pH became 9-10, to a 10% solution of tetra-n-butyl-ammonium-hydroxide. After dissolving of the deposit resulting from stirring the liquid at pH 9-10, the solution was filtered to remove impurities. Thereafter, the pH of the solution was adjusted to 4.80 with nitric acids having concentrations of 1N, 0.1N, and 0.0IN. The resulting solution was left to stand overnight at a temperature of 5° C. to separate a crystal. The crystal was extracted by filtering and was dried under reduced pressure. The resulting crude product was refined using a gel column. The resulting solution was reduced under pressure reduction, condensed to 10 ml and thereafter, until its pH became 9-10, a 10% solution of tetra-n-butyl-ammonium-hydroxide was added. After dissolving of the deposit resulting from stirring the liquid at pH 9-10, the solution was filtered to remove impurities. Thereafter, the pH of the solution was again adjusted to between 5.20 and 1.50 with nitric acids to obtain compounds which are different in ‘n’ (n: 0-4).
- 10 ml of dimethyl sulfamide were added to a flask and warmed up to a temperature of 80° C. Then, the dimethyl sulfoxide was, after being combined with 4 g of [RuCl3•nH2O], stirred for a time duration of ten minutes. The resulting solution was cooled down to room temperature, added to 50 ml of acetone, and left to stand for an hour at a temperature of 5° C. to separate a crystal. The crystal was extracted by filtering and dried, under vacuum, to obtain a copper-colored crystal.
- To a flask, 2 g of the Example 4-1 and 2 g (4.1 mmol) were added. The resulting mixture was, after being added to 500 ml of DMF, stirred for four hours at a temperature of 140° C. under argon. The mixture was cooled down to 120° C. and was stirred, after addition of 3.1 g (41 mmol)/100 ml of ammonium thiocyanate solution for 2 hours. Then, after cooling the reaction solution down to room temperature, the separated crystal was extracted by filtering, washed with water and dried under vacuum. 2 g of the resulting crude product, 2.4 g of tetra-n-butyl-ammonium-thiocyanate, and 30 ml of water were added into a beaker to stir. The resulting mixture was added, until its pH became 9-10, to a 10% solution of tetra-n-butyl-ammonium-hydroxide. After dissolving of the deposit resulting from stirring the liquid at pH 9-10, the solution was filtered to remove impurities. Thereafter, the pH of the solution was adjusted to 4.80 with nitric acids having concentrations of 1N, 0.1N, and 0.01N. The resulting solution was left standing overnight at a temperature of 5° C. to separate a crystal. The crystal was extracted by filtering and was dried under reduced pressure.
- The resulting crude product was melted and refined with a gel column. The resulting solution was, under pressure reduction, condensed to about 10 ml and added, until its pH became 9-10, to a 10% solution of tetra-n-butyl ammonium-hydroxide. After dissolving of the deposit resulting from stirring the liquid pH 9-10, the solution was filtered to remove impurities. Thereafter, the pH of the solution was again adjusted to between 5.20 and 1.50 with nitric acids to obtain a black crystal.
- The ruthenium complex of each of 4,4′-diethyl-[2,2′]bipyridine and, 4,4′,4″-triethyl-[2,2′;6′,2″]terpyridine is synthesized in a similar fashion as described in each of Examples 2 to 4. The ruthenium complex synthesized from the 4,4′-diethyl-[2,2′]bipyridine is a red crystal, while the ruthenium complex synthesized from the 4,4′,4″-triethyl-[2,2′;6′,2″]terpyridine is a green crystal.
- The structure of each of the above substances was identified by way of nuclear magnetic resonance analysis (NMR), ultraviolet visual ray spectroscopy (UV-VIS), high-speed liquid chromatography, mass spectrometry, and elemental analysis.
- (1) With respect to the Example 1, its NMR spectrum and IR spectrum are illustrated in FIG. 1 and FIG. 2, respectively. As apparent from FIG. 1, the peak of chemical shift δ 8.58 ppm (2H,d,J=4.9) corresponds to 6-position of hydrogen and 6′″-position of hydrogen, the peak of chemical shift δ 8.46 ppm (411,s) corresponds to 5′-position of hydrogen, 3″-position of hydrogen, 3′-position of hydrogen, and 5″-position of hydrogen, the peak of chemical shift δ 8.31 ppm (2H,d,j=1-6) corresponds to 3-position of hydrogen and 3 ′″-position of hydrogen, and the peak of chemical shift 67 7.17 ppm (2H,d,J=5.0;1,7) corresponds to 5-position of hydrogen and 5′″-position of hydrogen.
- And as apparent from FIG. 2, the peak of 3050 cm−1(w) and the peak of 3000-2800 cm−1(m) correspond to the pyridine and —CH2CH3. Thus, the present compound can be characterized by NMR spectrum and IR spectrum.
- In addition, the present compound can be characterized by mass spectrometry and elemental analysis.
- (2) With respect the Example 2, its NMR spectrum and IR spectrum are illustrated in FIG. 3 and FIG. 4, respectively.
- As apparent from FIG. 3, the peak of chemical shift δ 9.57 ppm (2H,d,J=,5.5) corresponds to 6-position of hydrogen and 6′″-position of hydrogen, the peak of chemical shift δ′ 8.92 ppm (2H, d,J=0.9) corresponds to 5′-position of hydrogen and 3″-position of hydrogen, the peak of chemical shift a δ0.88 ppm (2H,d,J−0.9) corresponds to the 3′-position of hydrogen and 5″-position of hydrogen, the peak of chemical shift δ 8.77 ppm (2H,d,J=0.9) corresponds to the 3-position of hydrogen and the 3′″-position of hydrogen, and the peak of shift δ8.25 ppm (2H,dd,J=5.5; 1.6) corresponds to the 5-position of hydrogen and 5′″-position of hydrogen.
- And as apparent from FIG. 4, the peak of 3600-2500 cm−1(b), the peak of 3073 cm−1(w), the peak of 3000-2900 cm−1(m), the peak of 2101 cm−1(s), the peak of 171.1 cm−1(m), and the peak of 1605 cm−1(m) corresponds to OH, pyridine skeleton, TBA, NCS, CO, and CO, respectively. Thus, the present compound can be characterized by NMR spectrum and IR spectrum.
- In addition, the compound of Example 2 can be characterized by mass spectrometry and elemental analysis.
- For convenience, FIG. 5 and FIG. 6 illustrate NMR spectrums of the respective derivatives of 4,4′-diethyl-[2,2′]bipyridine and of 4,4′,4″-triethyl-[2,2′;6′,2″]terpyridine.
- UV-VIS absorption spectroscopy of each complex of pyridine derivative
- Photoelectric Transfer Characteristic
- FIG. 7 shows the complex of ruthenium which is synthesized from each of the carbonic acid derivatives of pyridine dimer, pyridine trimer, and pyridine tetramer. The measurement of absorption spectrum was performed such that each compound was dissolved in ethanol. The colors of the respective pyridine dimer, pyridine trimer, and pyridine tetramer are red, green, and blue violet. As apparent from FIG. 7, whenever the polymerization degree of pyridine increases, its absorption wavelength shifts to a longer wavelength. Thus, a large overlap between the solar light spectrum and the spectrum of the compound (complex of pyridine tetramer derivative) in accordance with the present invention occurs. This proves that the complex of the pyridine tetramer derivative may be used as dye sensitizing element which makes it possible to increase photoelectric exchanging performance when compared to a complex of pyridine dimer or trimer derivative as dye sensitizing element.
- Japanese Patent Application No. 2000-389181, filed Dec. 21, 2000 (12th Year of Heisei) is incorporated herein by reference.
- Obviously, numerous modifications and variations on the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
Claims (10)
1. A pyridine compound represented by the following formula (I)
wherein each of R1, R2, R3, R4 is independently —OR′, —COOR′, —CONR′, —CHO, —CH2OR′, —CN, an alkyl group whose carbon number ranges from 1 to 20 inclusive, or —COONR′4, wherein R′ is a hydrogen, or an alkyl group whose carbon number ranges from 1 to 4 inclusive.
2. The pyridine compound according to claim 1 , wherein each of R1, R2, R3, R4 is an ethyl group or an isopropyl group.
3. The pyridine compound according to claim 1 , wherein each of R1, R2, R3, R4 is a carboxyl group or a carboxyl ester.
4. A complex of a pyridine compound represented by the following formula (II)
wherein each of X1, X2, X3, X4 is independently —OR, —COOR′, —CONR′, —CHO, —CH2OR′, —CN, an alkyl group whose carbon number ranges from 1 to 20- inclusive, or —COONR′4, wherein R′ is a hydrogen, or an alkyl group whose carbon number ranges from 1 to 4 inclusive;
wherein Z is Cl, Br, CN, NCS, or NCO; and
wherein M is Ru or Os.
5. The complex of the pyridine compound according to claim 4 , wherein X1 and X4 are the same and X2 and X3 are the same, respectively.
6. The complex according to claim 4 , wherein Z is NCS and M is Ru.
7. The complex according to claim 4 , wherein each of X1, X2, X3, X4 is independently a carboxyl group or an amid group.
8. The pyridine compound according to claim 1 , which is 4,4′,4″,4′″-tetraethyl-[2,2′;6′,2″6″,2′″] quaterpyridine, 4,4′,4″,4′″-tetraisopropyl [2,2′;6′2″;6″2′″]quarterpyridine, [2,2′;6′,2″;6″,2′″]quaterpyridine-4,4′,4″,4′″-tetracarboxylic acid, or [2,2′;6′,2″;6″,2′″]quaterpyridine-4,4′,4″,4′″-tetracarboxylic acid tetra ester.
9. The complex according to claim 4 , wherein M is Os.
10. A dye sensitizing solar battery, comprising:
a transparent substrate;
a transparent conductive membrane;
a conductive substrate opposed to the transparent substrate;
a set of sensitizing dye carrying semiconductor electrodes; and
a catalytic layer;
wherein said sensitizing dye is the complex according to claim 4.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000-389181 | 2000-12-21 | ||
JP2000389181A JP4691779B2 (en) | 2000-12-21 | 2000-12-21 | Pyridine derivatives and their complexes |
Publications (2)
Publication Number | Publication Date |
---|---|
US20020082422A1 true US20020082422A1 (en) | 2002-06-27 |
US6437130B1 US6437130B1 (en) | 2002-08-20 |
Family
ID=18855784
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/024,378 Expired - Lifetime US6437130B1 (en) | 2000-12-21 | 2001-12-21 | Pyridine derivative and its complex |
Country Status (4)
Country | Link |
---|---|
US (1) | US6437130B1 (en) |
JP (1) | JP4691779B2 (en) |
DE (1) | DE10163359B4 (en) |
GB (1) | GB2372035B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050139257A1 (en) * | 2003-12-26 | 2005-06-30 | Sharp Kabushiki Kaisha | Photosensitizing transition metal complex containing quaterpyridine and photovoltaic cell with the metal complex |
US20100101643A1 (en) * | 2007-03-29 | 2010-04-29 | Sumitomo Chemical Company, Limited | Compound, photoelectric converter and photoelectrochemical cell |
WO2010055471A1 (en) * | 2008-11-11 | 2010-05-20 | Ecole Polytechnique Federale De Lausanne (Epfl) | Novel anchoring ligands for sensitizers of dye-sensitized photovoltaic devices |
US20100218825A1 (en) * | 2007-04-06 | 2010-09-02 | Kyungpook National University Industry Academic Cooperation Foundation | Dye for dye-sensitized solar cell and Solar cell using it |
US20150280142A1 (en) * | 2014-04-01 | 2015-10-01 | Ricoh Company, Ltd. | Organic material and photoelectric conversion element |
US10392395B2 (en) | 2009-10-30 | 2019-08-27 | Sumitomo Chemical Company, Limited | Nitrogen-containing aromatic compounds and metal complexes |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4617771B2 (en) * | 2004-08-20 | 2011-01-26 | 株式会社豊田中央研究所 | Metal complex dye, photoelectrode and photosensitized solar cell |
JP4721755B2 (en) * | 2005-04-15 | 2011-07-13 | シャープ株式会社 | Complex, photoelectric conversion element and dye-sensitized solar cell |
KR101341299B1 (en) | 2006-07-05 | 2013-12-12 | 니폰 가야꾸 가부시끼가이샤 | Dye-sensitized solar cell |
KR101146668B1 (en) * | 2006-11-15 | 2012-05-23 | 삼성에스디아이 주식회사 | Dye for Photoelectronic Device And Photoelectronic Device Comprising the Dye |
JP2008266634A (en) * | 2007-03-29 | 2008-11-06 | Sumitomo Chemical Co Ltd | Compound, photoelectric transducer and photoelectrochemical battery |
EP2301932A1 (en) * | 2009-09-29 | 2011-03-30 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Novel ligands for sensitizing dyes of dye-sensitized solar cells |
JP5572028B2 (en) * | 2010-08-03 | 2014-08-13 | 富士フイルム株式会社 | Photoelectric conversion device, photoelectrochemical cell using the same, and composition for photoelectric conversion device |
JP2015029074A (en) * | 2013-07-05 | 2015-02-12 | 富士フイルム株式会社 | Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, ligand, solution of dye, dye adsorption electrode and dye-sensitized solar cell manufacturing method |
CN112079878A (en) * | 2020-09-23 | 2020-12-15 | 荆楚理工学院 | Preparation method of dichlorotetra (dimethyl sulfoxide) ruthenium metal organic compound |
CN112094300A (en) * | 2020-09-23 | 2020-12-18 | 荆楚理工学院 | Dicyano tetra-tert-butyl pyridine ruthenium metal organic compound, preparation method and application thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01207272A (en) * | 1988-02-12 | 1989-08-21 | Fuji Photo Film Co Ltd | Production of 4-hydroxyoligopyridines |
JPH01207271A (en) * | 1988-02-12 | 1989-08-21 | Fuji Photo Film Co Ltd | Production of 4-hydroxyoligopyridines |
GB9217811D0 (en) * | 1992-08-21 | 1992-10-07 | Graetzel Michael | Organic compounds |
-
2000
- 2000-12-21 JP JP2000389181A patent/JP4691779B2/en not_active Expired - Fee Related
-
2001
- 2001-12-20 GB GB0130463A patent/GB2372035B/en not_active Expired - Fee Related
- 2001-12-21 DE DE10163359A patent/DE10163359B4/en not_active Expired - Fee Related
- 2001-12-21 US US10/024,378 patent/US6437130B1/en not_active Expired - Lifetime
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050139257A1 (en) * | 2003-12-26 | 2005-06-30 | Sharp Kabushiki Kaisha | Photosensitizing transition metal complex containing quaterpyridine and photovoltaic cell with the metal complex |
US20100101643A1 (en) * | 2007-03-29 | 2010-04-29 | Sumitomo Chemical Company, Limited | Compound, photoelectric converter and photoelectrochemical cell |
US20100218825A1 (en) * | 2007-04-06 | 2010-09-02 | Kyungpook National University Industry Academic Cooperation Foundation | Dye for dye-sensitized solar cell and Solar cell using it |
WO2010055471A1 (en) * | 2008-11-11 | 2010-05-20 | Ecole Polytechnique Federale De Lausanne (Epfl) | Novel anchoring ligands for sensitizers of dye-sensitized photovoltaic devices |
US10392395B2 (en) | 2009-10-30 | 2019-08-27 | Sumitomo Chemical Company, Limited | Nitrogen-containing aromatic compounds and metal complexes |
US20150280142A1 (en) * | 2014-04-01 | 2015-10-01 | Ricoh Company, Ltd. | Organic material and photoelectric conversion element |
US9246110B2 (en) * | 2014-04-01 | 2016-01-26 | Ricoh Company, Ltd. | Organic material and photoelectric conversion element |
Also Published As
Publication number | Publication date |
---|---|
JP4691779B2 (en) | 2011-06-01 |
JP2002193935A (en) | 2002-07-10 |
US6437130B1 (en) | 2002-08-20 |
DE10163359B4 (en) | 2005-04-28 |
GB0130463D0 (en) | 2002-02-06 |
GB2372035A (en) | 2002-08-14 |
DE10163359A1 (en) | 2002-07-18 |
GB2372035B (en) | 2004-04-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6437130B1 (en) | Pyridine derivative and its complex | |
CN109054428B (en) | Preparation method of near-infrared cyanine dye | |
US7538217B1 (en) | Ruthenium complex | |
Meesala et al. | Synthesis, structures and electrochemical and photophysical properties of anilido-benzoxazole boron difluoride (ABB) complexes | |
CN106463272A (en) | Photosensitizer and photoelectric conversion element | |
CN113214217B (en) | Near-infrared xanthene fluorescent compound and preparation method thereof | |
CN113004313A (en) | Double-thiophene-double-coumarin-based BODIPY near-infrared fluorescent dye and preparation method thereof | |
US20140046064A1 (en) | Process for the Synthesis of Precursor Complexes of Titanium Dioxide Sensitization Dyes Based on Ruthenium Polypyridine Complexes | |
Lahav et al. | A new method of enantiomeric purification via a topochemical photodimerization reaction. Application to three 1-aryl ethanols | |
US5110916A (en) | Bis (octaalkylphthalocyaninate) lanthanides | |
CN115197260A (en) | Alkynyl coupled double-BODIPY near-infrared fluorescent dye with J aggregation effect and preparation method thereof | |
CN115215839A (en) | Indolyl benzimidazole near-infrared fluorescent dye and preparation method and application thereof | |
JPH0742411B2 (en) | Anthraquinone long-wavelength absorption dye | |
CN110818673B (en) | Synthesis method of cyclic methylene disulfonate | |
CN109053531B (en) | Asymmetric squarylium cyanine material and preparation method and application thereof | |
CN112898328A (en) | Coupled double-BODIPY fluorescent dye and preparation method thereof | |
JP2012007084A (en) | New photosensitizer | |
CN113072561A (en) | Synthesis method of long-wavelength asymmetric rhodamine dye | |
CN113150017A (en) | Coupled double-BODIPY near-infrared absorption dye and preparation method thereof | |
Elwood | Dyes containing the phenalene ring system. I. Synthesis of benzothiazole-containing dyes | |
CN112876873B (en) | Near-infrared two-region heptamethine cyanine dye and preparation method thereof | |
CN105131043B (en) | The phenthazine that one class is used for DSSC directly replaces bipyridyl ruthenium dye | |
CN112778375B (en) | Amphiphilic chiral platinum complex, self-assembled temperature-sensitive single-component luminescent material and application thereof | |
CN115850993B (en) | Chiral amphiphilic near-infrared aza-BODIPY dye and preparation method thereof | |
Malig et al. | Synthesis and characterization of novel" Clicked" dimers of unsymmetrically substituted tetraphenylporphyrins |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: AISIN SEIKI KABUSHIKI KAISHA, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PAIDI, REDDY YELLA;ITO, MASAYUKI;REEL/FRAME:012568/0516 Effective date: 20020201 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FPAY | Fee payment |
Year of fee payment: 12 |