TWI403514B - Photosensitive dye and its manufacturing method - Google Patents
Photosensitive dye and its manufacturing method Download PDFInfo
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- TWI403514B TWI403514B TW100101105A TW100101105A TWI403514B TW I403514 B TWI403514 B TW I403514B TW 100101105 A TW100101105 A TW 100101105A TW 100101105 A TW100101105 A TW 100101105A TW I403514 B TWI403514 B TW I403514B
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- hydrogen
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- carbazole
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- 238000004519 manufacturing process Methods 0.000 title claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 13
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 11
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical group [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000975 dye Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000010953 base metal Substances 0.000 claims description 12
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical class O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 11
- 150000003577 thiophenes Chemical class 0.000 claims description 11
- 125000006288 3,5-difluorobenzyl group Chemical group [H]C1=C(F)C([H])=C(C([H])=C1F)C([H])([H])* 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000000434 metal complex dye Substances 0.000 claims description 5
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 4
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- ZBFAXMKJADVOGH-UHFFFAOYSA-N 2-fluoro-4-methylpyridine Chemical compound CC1=CC=NC(F)=C1 ZBFAXMKJADVOGH-UHFFFAOYSA-N 0.000 claims description 3
- 150000007980 azole derivatives Chemical class 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 150000001556 benzimidazoles Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 13
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 4
- 150000001448 anilines Chemical class 0.000 claims 3
- 239000003446 ligand Substances 0.000 abstract description 17
- 239000003504 photosensitizing agent Substances 0.000 abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 150000003303 ruthenium Chemical class 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 150000002431 hydrogen Chemical group 0.000 description 16
- 125000002524 organometallic group Chemical group 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 6
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 6
- 150000003335 secondary amines Chemical class 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012327 Ruthenium complex Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- -1 organometallic ruthenium complexes Chemical class 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000002165 photosensitisation Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 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 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- JJWJFWRFHDYQCN-UHFFFAOYSA-J 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylate;ruthenium(2+);tetrabutylazanium;dithiocyanate Chemical compound [Ru+2].[S-]C#N.[S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 JJWJFWRFHDYQCN-UHFFFAOYSA-J 0.000 description 1
- XSGVVNHYXQQWQK-UHFFFAOYSA-N CNN(C)C.CNN(C)C.[Li] Chemical compound CNN(C)C.CNN(C)C.[Li] XSGVVNHYXQQWQK-UHFFFAOYSA-N 0.000 description 1
- IIDXFANDNVTHOR-UHFFFAOYSA-N COC(=O)C1(NC=CC=C1)C1=NC=CC(=C1)C(=O)OC Chemical compound COC(=O)C1(NC=CC=C1)C1=NC=CC(=C1)C(=O)OC IIDXFANDNVTHOR-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 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
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 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 Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hybrid Cells (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pyridine Compounds (AREA)
Description
本發明是有關於一種太陽能電池光敏染料及其製造方法,特別是有關於一種可適用於染料敏化太陽能電池的含氮雜環碳烯-吡啶配位基之釕金屬錯合物染料及其製造方法。
近年來因為日益增加的能源需求與全球暖化的影響,使得可再生能源的研究發展吸引並獲得了各界的重視。而染料敏化太陽能電池(DSSC)符合便宜太陽能發電裝置的發展及需求並具有解決目前能源逐漸短缺問題的可能性。自Gratzel教授與其工作團隊在1991年發表染料敏化太陽能電池染料文獻以來,具聯或多吡啶配位基的釕金屬錯合物如N3、N719和Black Dye確實展現了不錯的光電轉換效率。因此,染料敏化太陽能電池的探討與研究引起不同領域之學者的興趣,亦導致各種類型的有機金屬釕錯合物染料、有機金屬非釕錯合物染料與純有機結構染料被廣泛研究。然而,迄今在染料敏化太陽能電池的應用上主要被報導的染料仍大多數以有機金屬釕錯合物為主,而這些錯合物染料一般使用聯吡啶或多吡啶為配位基團。
有鑑於此,本發明之目的就是在提供一種以含氮雜環碳烯(NHC)-吡啶為配位基的釕金屬錯合物染料並應用於染料敏化太陽能電池上,其具有高電流密度、高電壓以及優越的光電轉換效率等性質。
為達上述目的,本發明提供一種光敏染料光敏染料,此光敏染料為釕金屬配位化合物,該釕金屬配位化合物之分子式如式(I)與式(II),
其中,
其中,分子式(I)與式(II)中的X為Ra
、二級胺類衍生物、噻吩衍生物(n=1~2)、3,4-乙烯二氧噻吩衍生物(n=1~2)、苯胺衍生物或咔唑衍生物,其中Ra
、Rb
、Rc
、Rd
及Re
係各自為氫、C6
H5
、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)、SCi
H2i+1
(i=1~15)或咔唑衍生物。
其中,Y為Ra
、苯基衍生物、苯甲基衍生物或3,5-二氟苯甲基,其中Ra
係各自為氫、Cm
H2m +1
(m=1~15),其中Rf
及Rg
係各自為氫、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)、SCi
H2i+1
(i=1~15)。
其中,Z為Ra
、-COOH、-Rh
COOH、-CN、-CONH2
、-CONHRh
, -PO3
H2
、二級胺類衍生物、噻吩衍生物(n=1~2)、3,4-乙烯二氧噻吩衍生物(n=1~2)、苯胺衍生物或咔唑衍生物,其中Ra
、Rb
、Rc
、Rd
及Re
係各自為氫、C6
H5
、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)、SCi
H2i+1
(i=1~15)或咔唑衍生物,其中Rh
係各自為C6
H5
、Cm
H2m +1
(m=1~3)。
為達上述目的,本發明提供一種光敏染料,此光敏染料為釕金屬配位化合物,此釕金屬配位化合物之分子式為式(III),
其中,
其中,
其中,
其中,分子式(III)含碳烯多芳香環結構(G)可分別為Ⅲ-a、Ⅲ-b或Ⅲ-c結構的各類衍生物,其中Ri
、Rj
及Rk
係各自為氫、C6
H5
、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)、SCi
H2i+1
(i=1~15)、或咔唑衍生物其中Re
係各自為氫、C6
H5
、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)。
其中分子式(III)中的Y為Ra
、苯基衍生物、苯甲基衍生物或3,5-二氟苯甲基,其中Ra
係各自為氫、Cm
H2m +1
(m=1~15),其中Rf
及Rg
係各自為氫、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)、SCi
H2i+1
(i=1~15)。
其中,Z為Ra
、-COOH、-Rh
COOH、-CN、-CONH2
、-CONHRh
, -PO3
H2
、二級胺類衍生物、噻吩衍生物(n=1~2)、3,4-乙烯二氧噻吩衍生物(n=1~2)、苯胺衍生物或咔唑衍生物,其中Ra
、Rb
、Rc
、Rd
及Re
係各自為氫、C6
H5
、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)、SCi
H2i+1
(i=1~15)或咔唑衍生物,其中Rh
係各自為C6
H5
、Cm
H2m +1
(m=1~3)。
為達本發明之目的,提供一種光敏染料之製造方法,至少包括:使苯並咪唑(benzimidazole)與2-氟-4-甲吡啶反應,並隨之以1-溴辛烷進行烷化取代反應形成一苯並咪唑衍生物之鹽類;以及使該鹽類與含氮雜環碳烯-吡啶、硫氰酸根離子等試劑進行錯合反應合成相對應的甲基脂衍生物,其再經水解以獲得具碳烯-吡啶、聯吡啶、硫氰酸根配位基之釕金屬錯合物染料。
承上所述,依本發明之一種光敏染料,其可具有下述優點:本發明之光敏染料為釕金屬配位化合物,其特徵在於利用碳取代傳統聯吡啶配位基上其中的一個氮,例如以含氮雜環碳烯-吡啶配位基取代傳統聯吡啶配位基。此外,相對於具有兩個不同結構配位基的雙螯合基(bidentate ligands)釕金屬錯合物染料而言,本發明具有簡易合成與適合大量製備的特色。相較於傳統之N719,本發明之含碳烯有機金屬釕光敏染料確實具有較佳的短路電流(Jsc
)、開路電壓(Voc
)以及光電轉換效率。再者,本發明係使用含氮雜環碳烯-吡啶配位基,因為此類碳烯配位基具獨特的電子特性且其有機金屬錯合物具相當的穩定度故可進一步藉由優化含碳烯-吡啶配位基的結構而達到提昇光電轉換效率。
茲為使貴審查委員對本發明之技術特徵及所達到之功效有更進一步之瞭解與認識,謹佐以較佳之實施例及配合詳細之說明如後。
以下將參照相關圖式,說明依本發明之光敏染料之較佳實施例,為使便於理解,下述實施例中之相同元件係以相同之符號標示來說明。
本發明之光敏染料為以含氮雜環碳烯-吡啶配位基取代傳統聯吡啶配位基的釕金屬配位化合物,與具有兩個不同結構配位基的雙螯合基釕金屬錯合物染料比較,本發明的染料較易合成且適合大量製備。氮雜環碳烯具獨特的電子特性且其在本發明之前並未被用於合成提供當染料敏化太陽能電池使用的具硫氰酸根配位之有機金屬釕光敏染料。若再優化含氮雜環碳烯-吡啶配位基上的取代基結構,本發明之光敏染料可具更優越的光電轉換效率。
本發明之光敏染料之第一種實施例為釕金屬配位化合物,此釕金屬配位化合物之分子式如式(I)與式(II),
其中,
其中,分子式(I)與式(II)中的X為Ra
、二級胺類衍生物、噻吩衍生物(n=1~2)、3,4-乙烯二氧噻吩衍生物(n=1~2)、苯胺衍生物或咔唑衍生物,其中Ra
、Rb
、Rc
、Rd
及Re
係各自為氫、C6
H5
、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)、SCi
H2i+1
(i=1~15)或咔唑衍生物。
其中,Y為Ra 、苯基衍生物、苯甲基衍生物或3,5-二氟苯甲基,其中Ra 係各自為氫、Cm H2m +1 (m=1~15),其中Rf 及Rg 係各自為氫、Cm H2m +1 (m=1~15)、OCP H2P+1 (p=1~15)、SCi H2i+1 (i=1~15)。
其中,Y為Ra 、苯基衍生物、苯甲基衍生物或3,5-二氟苯甲基,其中Ra 係各自為氫、Cm H2m +1 (m=1~15),其中Rf 及Rg 係各自為氫、Cm H2m +1 (m=1~15)、OCP H2P+1 (p=1~15)、SCi H2i+1 (i=1~15)。
其中,Z為Ra
、-COOH、-Rh
COOH、-CN、-CONH2
、-CONHRh
,-PO3
H2
、二級胺類衍生物、噻吩衍生物(n=1~2)、3,4-乙烯二氧噻吩衍生物(n=1~2)、苯胺衍生物或咔唑衍生物,其中Ra
、Rb
、Rc
、Rd
及Re
係各自為氫、C6
H5
、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)、SCi
H2i+1
(i=1~15)或咔唑衍生物,其中Rh
係各自為C6
H5
、Cm
H2m +1
(m=1~3)。
為達上述目的,本發明提供一種光敏染料,此光敏染料為釕金屬配位化合物,此釕金屬配位化合物之分子式為式(III),
其中,
其中,
其中,
其中,分子式(III)含碳烯多芳香環結構(G)可分別為Ⅲ-a、Ⅲ-b或Ⅲ-c結構的各類衍生物,其中Ri
、Rj
及Rk
係各自為氫、C6
H5
、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)、SCi
H2i+1
(i=1~15)、或咔唑衍生物其中Re
係各自為氫、C6
H5
、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)。
其中分子式(III)中的Y為Ra
、苯基衍生物、苯甲基衍生物或3,5-二氟苯甲基,其中Ra
係各自為氫、Cm
H2m +1
(m=1~15),其中Rf
及Rg
係各自為氫、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)、SCi
H2i+1
(i=1~15)。
其中,Z為Ra
、-COOH、-Rh
COOH、-CN、-CONH2
、-CONHRh
, -PO3
H2
、二級胺類衍生物、噻吩衍生物(n=1~2)、3,4-乙烯二氧噻吩衍生物(n=1~2)、苯胺衍生物或咔唑衍生物,其中Ra
、Rb
、Rc
、Rd
及Re
係各自為氫、C6
H5
、Cm
H2m +1
(m=1~15)、OCP
H2P+1
(p=1~15)、SCi
H2i+1
(i=1~15)或咔唑衍生物,其中Rh
係各自為C6
H5
、Cm
H2m +1
(m=1~3)。
以下將列舉本發明之光敏染料之一種例子,其分子式CBTR如下:
本發明之合成實例分子式CBTR其製備流程如下詳示,但以下之合成實施例並非限制本發明之範圍。
反應式(1)
如反應式(1),此CBTR之製備方法為首先將苯並咪唑(benzimidazole) (2.0 g,16.93 mmol)以及2-氟-4-甲吡啶(2-fluoro-4-methylpyridine)(2.27 mL,22 mmol)與碳酸鉀(potassium carbonate)(K2
CO3
) (1.75 g,12.7 mmol)置入反應瓶中,並且在氬氣的環境下將二甲基甲醯胺(DMF) (34 mL,0.5 M)注入反應瓶中,溫度維持為140 ℃,反應時間則為24小時。待反應完後,利用減壓蒸餾法除去DMF而獲得褐色固體。接著,使用CH2
Cl2
(200 mL)溶解此褐色固體,並用200mL蒸餾水分三次萃取,其中有機層以無水硫酸鈉(sodium sulfate)除水。後續,使用迴旋濃縮法進行乾燥步驟藉以獲得白色固體產物(3.1 g)。之後,將所得的白色固體產物(3.1g,14.82 mmol)置入反應瓶中,並且在氬氣的環境下將DMF (5.3 mL,0.45 M)與1-溴辛烷(1-bromooctane)(3.83 mL,14.82 mmol)注入反應瓶中。接著,進行迴流反應約24小時。待反應完後,利用蒸餾法去除DMF,而獲得褐色固體,之後利用620 mL 己烷/CH2
Cl2
產生結晶析出,待過濾後使其乾燥即可得到淡褐色固體化合物2 (0.9 g)。
反應式(2)
在反應式(2)中,將化合物2(5.6g,13.94 mmol)與二氯(p-甲基丙苯)釕二聚體{[RuCl2
(p-cymene)]2
}(3.9 g,6.33 mmol)置入反應瓶中,並且在氬氣的環境下將CH2
Cl2
(700 mL,0.02 M)注入反應瓶中,且於-30 ℃的環境下攪伴一小時。之後,將雙(三甲基矽)醯胺鋰(LHMDS) (16 mL、16 mmol)注入反應瓶並進行反應約8小時。之後,使環境溫度回到室溫。將CH2
Cl2
抽乾後再將2,2`-聯吡啶-4,4`-二羧酸甲酯(4,4’-bis(methoxycarbonyl)- 2,2’-bipyridine) (1.34 g,4.79 mmol)加入反應瓶中。之後,在氬氣的環境下將ClCH2
CH2
Cl(160 mL,0.025 M)注入反應瓶並且在80 ℃的溫度下攪拌反應6小時。待反應完後,除去溶劑並直接加入硫氰酸鉀(potassium thiocyanate)(7.77 g,29.37 mmol)。緊接著注入H2
O/DMF:1/9 (105 mL,0.02 M)。並於80 ℃下攪拌反應24小時。待反應完後,利用減壓蒸餾法除去DMF,並以CH2
Cl2
(500 mL)溶解,再以100 mL蒸餾水分三次萃取,其中有機層用無水硫酸鈉(sodium sulfate)除水。後續,使用迴旋濃縮法進行乾燥步驟並使用管柱層析法藉以分離出黑色固體產物(0.83 g)。
反應式(3)
在反應式(3)中,將化合物3 (0.83 g,1.03 mmol)與氫氧化鋰(LiOH) (0.1 g,2.54 mmol)置入反應瓶中並注入H2
O/EtOH:1/9 (50 mL,0.02 M),於室溫下攪拌6小時。反應完後,使用迴旋濃縮法除去EtOH。接著,加入166 mL蒸餾水,隨後以0.1 M的HCl水溶液調至pH1(約加入3 eq.,31 mL)使其產生固體沉澱。待將此固體沉澱離心處理後,倒出澄清液體。之後,將離心處理後所沉澱的固體以DCM/MeOH作動相,再以LH20管柱純化藉以分離出黑色產物(0.68 g,85%)。
經列表後,本發明之CBTR以及傳統之N719染料製造之染料敏化電池之電流、電壓、光電轉換效率量測結果,如表1所示。由表1可知,相較於傳統之N719,本發明之CBTR染料確實具有較佳的短路電流(Jsc
)、開路電壓(Voc
)以及光電轉換效率。且本發明之碳烯有機金屬釕光敏染料於薄膜吸收光譜亦顯示其較傳統的具雙聯吡啶配位基的N719更貼近大陽光圖譜,顯示此類含碳烯染料之高潛能及應用性。
表1
此外,這一類新穎的碳烯有機金屬釕光敏染料除可提供當太陽能電池的光學增感劑(photosensitizer)使用外,本發明之含碳烯光敏染料有機金屬釕錯合物亦可應用於陰離子偵測器,使用於偵測如汞、鎘等重金屬有害離子。
以上所述僅為舉例性,而非為限制性者。任何未脫離本發明之精神與範疇,而對其進行之等效修改或變更,均應包含於後附之申請專利範圍中。
無。
無。
Claims (4)
- 一種光敏染料,至少包括:該光敏染料為釕金屬配位化合物,該釕金屬配位化合物之分子式為式(I),
- 一種光敏染料,至少包括:該光敏染料為釕金屬配位化合物,該釕金屬配位化合物之分子式為式(II),
- 一種光敏染料,至少包括:該光敏染料為釕金屬配位化合物,該釕金屬配位化合物之分子式為式(III),
- 一種光敏染料之製造方法,至少包括:使苯並咪唑(benzimidazole)與2-氟-4-甲吡啶反應,並隨之以1-溴辛烷進行烷化取代反應形成一苯並咪唑衍生物之鹽類;以及使該鹽類與含氮雜環碳烯-吡啶、硫氰酸根離子等試劑進行錯合反應合成相對應的甲基脂衍生物;最後其再經水解以獲得含氮雜環碳烯-吡啶之釕金屬錯合物染料。
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