CN110423486A - 三苯胺类有机染料及其合成方法 - Google Patents
三苯胺类有机染料及其合成方法 Download PDFInfo
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- CN110423486A CN110423486A CN201910676991.8A CN201910676991A CN110423486A CN 110423486 A CN110423486 A CN 110423486A CN 201910676991 A CN201910676991 A CN 201910676991A CN 110423486 A CN110423486 A CN 110423486A
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- organic dyestuff
- dyestuff
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- 239000000975 dye Substances 0.000 title claims abstract description 70
- 150000001412 amines Chemical class 0.000 title claims abstract description 19
- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims abstract description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 241001597008 Nomeidae Species 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 66
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000000605 extraction Methods 0.000 claims description 22
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- 239000007832 Na2SO4 Substances 0.000 claims description 20
- 239000003480 eluent Substances 0.000 claims description 20
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- 239000012044 organic layer Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
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- 239000000376 reactant Substances 0.000 claims description 8
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- 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 7
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl chloride Substances ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 7
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- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 claims description 6
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- 230000035484 reaction time Effects 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- IZPYBIJFRFWRPR-UHFFFAOYSA-N tert-butyl pyrrole-1-carboxylate Chemical class CC(C)(C)OC(=O)N1C=CC=C1 IZPYBIJFRFWRPR-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
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- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 4
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- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract description 3
- 230000021615 conjugation Effects 0.000 abstract description 2
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 2
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- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
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- BFJMHTOBRRZELQ-UHFFFAOYSA-N 3-iodo-2h-pyrazolo[3,4-c]pyridine Chemical compound N1=CC=C2C(I)=NNC2=C1 BFJMHTOBRRZELQ-UHFFFAOYSA-N 0.000 description 3
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- 125000000217 alkyl group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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- 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
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Abstract
本发明公开了一种三苯胺类有机染料及其合成方法。所述的三苯胺类有机染料的化学结构通式如式(1)所示:式中,R1选自氢基或苯已烯基,R2选自氢基或苯已烯基,为喹喔啉衍生物。本发明的三苯胺类有机染料具有长的共轭D‑π‑A结构,同时分子中含有氰基和羧基,吸电子基团是氰基乙酸,可作为太阳能电池敏化剂,在染料敏化太阳能电池中具有良好的应用前景。
Description
技术领域
本发明属于染料敏化太阳能电池敏化剂技术领域,涉及一种三苯胺类有机染料及其合成方法,具体涉及一种以三苯胺(TPA)结构单元为基础并通过共轭π-桥、双键和D-A-π-A引入苯基或喹喔啉单元等供电子基团的有机染料及其合成方法。
背景技术
太阳能作为来源最为广泛的绿色能源,提高太阳能的利用率有望缓解现有传统能源资源紧张以及尤其引起的温室效应的问题。太阳每小时产生3.8×1023千瓦时的能量,其中,每天有1.7×105TW的太阳能能到达地球上,有三分之一被反射回太空,也就是说每小时地球表面所接受的太阳能比人类一年中使用的能量多得多。太阳能作为来源最为广泛的绿色能源,提高太阳能的利用率有望缓解现有传统能源资源紧张以及由其引起的温室效应的问题。
目前光伏电池的转换效率都远低于理论值。如何有效的提高对太阳能的利用效率,是解决环境问题和能源短缺的一个重要途径。因此迫切需要开发一种能够将太阳光转化为电能的技术和材料。染料敏化太阳能电池(DSSCS)与传统的太阳电池相比,具有以下优点:(1)寿命长,使用寿命可达15-20年;(2)结构简单、易于制造,生产工艺简单,易于大规模工业化生产;(3)制备电池耗能较少,能源回收周期短;(4)生产成本较低,仅为硅太阳能电池的1/5~1/10,预计每峰瓦的电池的成本在10元以内;(5)生产过程中无毒无污染。
作为电池的重要组成部分,光敏剂染料能够有效地吸收太阳光,并由此产生激发电子,然后注入到二氧化钛等半导体的导带中,因此染料的光电性能对染料敏化太阳能电池的光电转换效率有着至关重要的影响。目前,基于钌配合物的染料敏化太阳能电池的光电转换效率可达11%,但由于其价格高昂、污染较大等方面的缺点限制了它的实际应用。
文献1报道了一种噻吩上的不同取代基对染料性能和电池的影响。由于烷烃链的增加,染料在TiO2表面的吸附减少,使得Jsc较低,且电子注入效率低,故该染料的光电转换效率降低(SAKONG C,KIM S H,YUK S B.et al.Influence of solvent and bridgestructure in alkylthio-substituted triphenylamine dyes on the photovoltaicproperties of dye sensitized solar cells[J].Chem Asian J.2012,7;1817-1826.)。
文献2报道了一种将噻唑[3,4-c]吡啶引人到三苯胺和氰基乙酸之间,并测试了3个不同供电子基团D-A-π-A结构的染料的光电性能。吸电子基团噻唑[3,4-c]吡啶的引人可以调控HOMO和LUMO能级差井使吸收光谱红移,但光电转换效率较低(HUA Y,WANG H D,ZHUX J,et al.New simple panchromatic dyes based on thiadiazolo[3,4-c]pyridineunit for dye-sensitized solar cells[J].Dyes and Pigments,2014,102;196-203)。
发明内容
本发明的目的在于提供一种三苯胺类有机染料及其合成方法。
实现本发明目的的技术方案如下:
三苯胺类有机染料,化学结构通式如式(1)所示:式中,R1选自氢基或苯已烯基,R2选自氢基或苯已烯基,为喹喔啉衍生物。
具体地,在本发明的具体实施方式中,所述的三苯胺类有机染料为
本发明还提供上述三苯胺类有机染料的合成方法,具体步骤如下:
步骤1,氮气保护下,以四(三苯基膦)钯为催化剂,在四氢呋喃存在下,将化合物A和1-Boc-吡咯-2-硼酸和水混合,回流反应,经Suzuki偶联反应制备化合物B,所述的化合物A选自合成路线如下:
步骤2,氮气保护下,在四氢呋喃存在下,在化合物B中加入甲醇钠和甲醇,经水解反应制备化合物C,合成路线如下:
步骤3,在N,N-二甲基甲酰胺(DMF)存在下,化合物C和溴代异辛烷发生取代反应制备D,合成路线如下:
步骤4,氮气保护下,在DMF存在下,将化合物D和POCl3混合,回流经Vilsmeier-Haak反应制备E,合成路线如下:
步骤5,在氮气保护下,在氯仿存在下,将化合物E和氢乙酸混合,回流经Knoevenagel缩合反应制备目标化合物三苯胺类有机染料,合成路线如下:
进一步地,步骤1中,所述的化合物A与1-Boc-吡咯-2-硼酸以及碳酸钠的摩尔比为1:2.2:3。
进一步地,步骤1中,所述的催化剂四(三苯基膦)钯的物质的量是化合物A的6%。
进一步地,步骤1中,所述的回流反应温度为60~80℃,所述的回流反应时间为12h以上。
进一步地,步骤2中,所述的化合物B与甲醇钠的摩尔比为1:4。
进一步地,步骤2中,所述的水解反应时间为2h以上。
进一步地,步骤3中,所述的化合物C与溴代异辛烷和NaH摩尔比为1:2.2:5。
进一步地,步骤3中,所述的反应时间为2h以上。
进一步地,步骤4中,所述的化合物D与N,N-二甲基甲酰胺以及POCl 3的物质的量比为2:1:3.7。
进一步地,步骤4中,所述的反应时间为2h以上。
进一步地,步骤5中,所述的化合物E与氰基乙酸摩尔比为1:3.9。
进一步地,步骤5中,所述的反应时间为4h以上。
进一步地,步骤5中,目标产物通过以下步骤进行后处理:反应完全后,向反应物中加入水,用CH2Cl2萃取,有机相用饱和NaCl溶液洗涤,有机层用无水Na2SO4干燥并旋转蒸发,DCM/MeOH作洗脱剂,柱层析得到有机染料。
与现有技术相比,本发明具有以下优点:
本发明方法反应条件温和、后处理简单方便,且产率达到80%以上。本发明合成的三苯胺类有机染料具有长的共轭D-π-A结构,同时分子中含有氰基和羧基,吸电子基团是氰基乙酸。本发明的染料中的羧基可以和半导体纳米以化学键的形式结合,有助于染料固定在电池中,同时还有利于电子的传输,再加上共轭长度的增加,使其成为太阳能电池敏化剂较为理想的材料,在染料敏化太阳能电池领域中具有良好的应用前景。
附图说明
图1为基于三苯胺类染料的DSSCs的J-V曲线。
具体实施方式
下面结合具体实施例和附图对本发明作进一步详述。
本实施例的染料的合成路线如下:
染料FWD 9的合成路线:
染料FWD 10的合成路线:
染料FHD 7的合成路线:
实施例1
染料FWD 9的合成:
化合物1的合成:在氮气氛下,将4-溴三苯胺(1.3030g,4mmol)溶解在无水N,N-二甲基甲酰胺(DMF)(9.3mL)中,在0℃下搅拌15min,向该溶液中逐滴加入POCl3(8mL,100mmol),溶液逐渐呈青黄色且有固体产生,继续在0℃下搅拌15min,随后将混合物在100℃反应20h。反应完全后,在0℃下向反应体系中逐滴加入水,过滤得到滤渣,滤渣用CH2Cl2萃取,将有机层用饱和NaCl水溶液洗涤,用无水Na2SO4干燥,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体1(淡黄色晶体,1.1353g),收率为74.6%。
化合物2的合成:在氮气氛下,将中间体1(1.2383g,3.3mmol)和苄基膦酸二乙酯(1.5483g,9.9mmol)溶解在DMF(9.2mL)中,在常温下搅拌30min,向混合溶液中加入叔丁醇钾(2.5717g,33mmol)常温反应2h。反应完全后,加入饱和NH4Cl溶液,用CH2Cl2萃取,将有机层用无水Na2SO4干燥并旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体2(黄色固体,1.6405g),收率为94.1%。
1H NMR(300MHz,CDCl3)δ7.50(d,J=7.8Hz,2H),7.42(d,J=8.4Hz,2H),7.39-7.30(m,3H),7.25(t,J=7.1Hz,1H),7.10(d,J=7.2Hz,1H),7.12-6.94(m,4H).
化合物3的合成:在50mL的两口烧瓶中依次加入中间体2(1.3567g,2.6mmol)、1-Boc-吡咯-2-硼酸(1.2098g,5.7mmol)、四(三苯基膦)钯(188.6mg,6%mmol),碳酸钠(857.3mg,7.8mmol),在氮气保护条件下,分别加入溶剂四氢呋喃(18.6mL)和水(4.7mL),将反应体系回流过夜。反应完全后,加入饱和NH4Cl溶液,用CH2Cl2萃取,有机相用无水Na2SO4干燥,过滤,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体3(黄色固体,1.3994g),收率为86.2%。
M.p:189-191℃.1H NMR(500MHz,CDCl3)δ(ppm):7.50(d,J=7.4Hz,4H),7.42(d,J=8.6Hz,4H),7.35(t,J=7.7Hz,4H),7.27-7.22(m,4H),7.15-7.09(m,6H),7.07(d,J=16.3Hz,2H),7.02(d,J=16.3Hz,2H),6.23(t,J=3.2Hz,1H),6.20(dd,J=3.2,1.8Hz,1H),1.44(s,9H).13C NMR(126MHz,CDCl3)δ(ppm):149.49,146.88,146.20,137.56,134.66,132.09,130.11,129.19,128.65,128.07,127.40,126.33,124.20,123.33,122.60,114.36,110.59,83.62,27.74.
化合物4的合成:在氮气氛中,将中间体3(1.3916g,2.2mmol)溶解在四氢呋喃(20mL)中,向该溶液中加入由甲醇钠(479.5mg,8.8mmol)和甲醇(20ml)的混合溶液,回流反应2h。反应完全后,用CH2Cl2萃取,将有机层用饱和NaCl水溶液洗涤,用无水Na2SO4干燥,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体4(黄色固体,1.0671g),收率为93.4%。
M.p:104-106℃.1H NMR(500MHz,CDCl3)δ(ppm):8.38(s,1H),7.51(d,J=7.5Hz,4H),7.42(d,J=8.6Hz,4H),7.39(d,J=8.6Hz,2H),7.36(t,J=7.7Hz,4H),7.29-7.22(m,2H),7.14(d,J=8.6Hz,2H),7.11(d,J=8.5Hz,4H),7.08(d,J=16.3Hz,2H),7.02(d,J=16.3Hz,2H),6.85(br,1H),6.48(br,1H),6.30(dd,J=5.7,2.7Hz,1H).13C NMR(126MHz,CDCl3)δ(ppm):146.80,145.35,137.56,131.97,131.82,128.66,128.07,127.44,127.33,126.34,125.04,124.78,123.93,118.60,110.12,105.56.
化合物5的合成:在氮气氛下,将中间体4(1.0046g,2.0mmol)溶解在无水DMF(14ml)中。在0℃下向该溶液中加入NaH(60%的矿物油分散体,645.2mg,10mmol)并在相同温度下搅拌15min。逐滴加入溴代异辛烷(851.2mg,4.4mmol)并将溶液在0℃下搅拌30min。然后将反应混合物转移至室温搅拌15h后,将反应物加热至60℃并搅拌30min。反应完全后,加入饱和NH4Cl溶液,用CH2Cl2萃取,将有机层用无水Na2SO4干燥并旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体5(黄色固体,710mg),收率为58%。
M.p:39-41℃.1H NMR(500MHz,CDCl3)δ(ppm):7.51(d,J=7.6Hz,4H),7.43(d,J=8.5Hz,4H),7.36(t,J=7.6Hz,4H),7.28(d,J=8.5Hz,2H),7.25(t,J=7Hz,2H),7.15(d,J=8.5Hz,2H),7.12(d,J=8.5Hz,4H),7.09(d,J=16.5Hz,2H),7.03(d,J=16.5Hz,2H),6.72(br,1H),6.20-6.12(m,2H),3.91-3.78(m,2H),1.55(br,1H),1.24-1.07(m,8H),0.86(t,J=7.3Hz,3H),0.74(t,J=7.3Hz,3H).13C NMR(126MHz,CDCl3)δ(ppm):146.80,145.85,137.50,134.07,131.98,129.97,128.87,128.62,128.02(s),127.41,127.30,126.30,124.15,124.03,122.64,108.61,107.30,50.95,40.81,30.41,28.37,23.63,22.84,14.02,10.45.
化合物6的合成:在氮气氛下,将中间体5(400.3mg,0.6mmol)溶解在无水氯仿(1.9mL)中,在0℃下,向该溶液中逐滴加入由N,N-二甲基甲酰胺(84.3mg,0.3mmol)和POCl3(275.9mg,1.1mmol)在氯仿(1.9mL)中制备的Vilsmeier试剂。将混合物在0℃下搅拌30min,然后升温至室温搅拌30min,最后回流30min。冷却后,向该溶液中加入乙酸钠(315.1mg,3.6mmol)的水溶液(3.8mL)并在80℃下搅拌15min。冷却后,向反应物中加水进行淬灭。用CH2Cl2萃取,将有机层用饱和NaHCO 3水溶液洗涤,用无水硫酸钠干燥,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体6(黄色固体,172.4mg),收率为41.2%。
M.p:61-63℃.1H NMR(500MHz,CDCl3)δ(ppm):9.54(s,1H),7.51(d,J=7.5Hz,4H),7.45(d,J=8.5Hz,4H),7.36(t,J=7.8Hz,4H),7.50-7.25(m,4H),7.18(d,J=8.5Hz,2H),7.13(d,J=8.5Hz,4H),7.09(d,J=16.5Hz,2H),7.04(d,J=16.5Hz,2H),6.99(d,J=4.0Hz,1H),6.27(d,J=4.0Hz,1H),4.39(d,J=7.0Hz,2H),1.61-1.54(m,1H),1.21-1.12(m,2H),1.11-0.99(m,6H),0.84(t,J=7.3Hz,3H),0.66(t,J=7.3Hz,3H).13C NMR(126MHz,CDCl3)δ(ppm):179.07,147.43,146.39,144.60,137.38,132.83,132.60,130.19,128.64,127.86,127.68,127.51,127.42,126.33,125.97,125.40,124.54,123.33,111.00,49.23,40.55,29.98,28.11,23.17,22.86,13.97,10.24.
染料FWD 9的合成:在氮气氛下,将中间体6(233.6mg,0.36mmol)、氰基乙酸(121.4mg,1.4mmol)和乙酸铵(11.1mg)溶解在甲苯(18.6mL)中,随后向混合溶液中加入冰乙酸(6.5ml),将混合物回流4小时。反应完全后,向反应物中加入水,用CH2Cl2萃取,将有机层用饱和NaCl水溶液洗涤,有机层用无水Na2SO4干燥并旋转蒸发,DCM/MeOH作洗脱剂,柱层析得到染料FWD9(橙色固体,209.7mg),收率为79.2%。
M.p:203-206℃.1H NMR(500MHz,CDCl3)δ(ppm):8.19(s,1H),7.89(br,1H),7.51(d,J=7.5Hz,4H),7.46(d,J=8.5Hz,4H),7.36(t,J=7.5Hz,4H),7.29-7.23(m,4H),7.18(d,J=8.0Hz,2H),7.13(d,J=8.5Hz,4H),7.09(d,J=17Hz,2H),7.04(d,J=16Hz,2H),6.46(br,1H),4.10(br,2H),1.54(br,1H),1.23-0.97(m,8H),0.85(t,J=6.8Hz,3H),0.71(t,J=7.0Hz,3H).13C NMR(126MHz,CDCl3)δ(ppm):169.78,147.89,146.26,145.26,140.69,137.40,132.93,130.11,128.69,128.19,127.87,127.60,127.52,126.38,125.34,124.80,123.12,121.17,117.34,114.35,47.83,41.85,30.32,28.15,23.61,22.80,13.91,10.39.HRMS(ESI,m/z):Calcd for[M-CO2H]-C50H46N3O3 -:720.3596,found:720.3605.
实施例2
染料FWD10的合成:
化合物7的合成:在250mL的两口烧瓶中依次加入4-溴苯胺(1.4516g,4.5mmol)、1-Boc-吡咯-2-硼酸(863.3mg,4.1mmol)、四(三苯基膦)钯(284.3mg,6%mmol),碳酸钠(1.3037g,13.5mmol),在氮气保护条件下,分别加入溶剂四氢呋喃(52mL)和水(13mL),将反应体系回流过夜。反应完全后,加入饱和NH4Cl溶液,用CH2Cl2萃取,有机相用无水Na2SO4干燥,过滤,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体7(白色固体,1.3061g),收率为70.7%
1H NMR(500MHz,CDCl3)δ(ppm):7.34(dd,J=3.2,1.8Hz,1H),7.25(t,J=7.6Hz,4H),7.20(d,J=8.5Hz,2H),7.11(d,J=7.7Hz,4H),7.04(d,J=8.5Hz,2H),7.01(t,J=7.3Hz,2H),6.21(t,J=3.3Hz,1H),6.17(dd,J=3.1,1.8Hz,1H),1.41(s,9H).
化合物8的合成:在100mL的两口烧瓶中加入中间体7(1.2849g,3.1mmol),在氮气保护下,向两口瓶中加入到CH2Cl2(15.5ml)中,在常温下搅拌使中间体1完全溶解在CH2Cl2中,随后在0℃下加入三氟乙酸(46.5ml),并在该温度下搅拌10min后,将反应转移至室温搅拌2h。反应完全后,在0℃下向反应体系中加入碳酸氢钠,使体系的pH在8~9左右,用CH2Cl2萃取,有机相用无水Na2SO4干燥,过滤,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体8(白色固体,351.8mg),收率为36.6%。
1H NMR(500MHz,CDCl3)δ(ppm):8.35(s,1H),7.35(d,J=8.6Hz,2H),7.25(t,J=7.9Hz,4H),7.10(d,J=8.8Hz,4H),7.09(d,J=8.8Hz,2H),7.02(t,J=7.3Hz,2H),6.84(dd,J=3.9,2.6Hz,1H),6.45(t,J=3.6Hz,1H),6.29(dd,J=5.9,2.7Hz,1H).
化合物9的合成:在氮气氛下,将中间体8(351.8mg,1.1mmol)溶解在无水DMF(8ml)中。在0℃下向该溶液中加入NaH(60%的矿物油分散体,363mg,8.8mmol)并在相同温度下搅拌15min。逐滴加入溴代异辛烷(653.8mg,3.3mmol)并将溶液在0℃下搅拌30min。然后将反应混合物转移至室温搅拌15h后,将反应混合物加热至60℃并搅拌30min。反应完全后,加入饱和NH4Cl溶液,用CH2Cl2萃取,将有机层用无水Na2SO4干燥并旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体9(透明液体,408.8mg),收率为90.9%。
1H NMR(500MHz,CDCl3)δ(ppm):7.26(t,J=7.9Hz,4H),7.23(d,J=8.7Hz,2H),7.11(d,J=7.8Hz,4H),7.08(d,J=8.5Hz,2H),7.02(t,J=7.3Hz,2H),6.70(t,J=2.0Hz,1H),6.17(t,J=3.1Hz,1H),6.14(dd,J=3.4,1.8Hz,1H),3.83(qd,J=13.9,7.3Hz,2H),1.56-1.50(m,1H),1.23-1.06(m,8H),0.74(t,J=7.4Hz,3H),0.72(t,J=7.4Hz,3H).13CNMR(126MHz,CDCl3)δ(ppm):147.67,146.52,134.21,129.90,129.20,128.16,124.26,123.50,122.78,122.47,108.44,107.20,50.93,40.78,30.40,28.36,23.64,22.83,13.99,10.44.
化合物10的合成:在氮气氛下,将中间体9(408.8mg,1mmol)溶解在无水氯仿(3.0mL)中。在0℃下,向该溶液中逐滴加入由DMF(109.7mg,1.5mmol)和POCl3(275.9mg,1.8mmol)在氯仿(3.0mL)中制备的Vilsmeier试剂。将混合物在0℃下搅拌30min,然后升温至室温,在室温下搅拌30min,最后回流30min。冷却后,向该溶液中加入乙酸钠(492.1mg,6mmol)的水溶液(7mL)并在80℃下搅拌15min。冷却后,向反应物中加入水进行淬灭。用CH2Cl2萃取,将有机层用饱和NaHCO 3水溶液洗涤,用无水Na2SO4干燥,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体10(淡黄色固体,380.7mg),收率为73.7%。
M.p:65-67℃.1H NMR(500MHz,CDCl3)δ(ppm):9.53(s,1H),7.29(t,J=7.9Hz,4H),7.24(d,J=8.6Hz,2H),7.14(dd,J=8.4,0.8Hz,4H),7.11(d,J=8.6Hz,2H),7.07(t,J=7.3Hz,2H),6.98(d,J=4.0Hz,1H),6.25(d,J=4.0Hz,1H),4.38(d,J=5.6Hz,2H),1.61-1.53(m,1H),1.20-1.11(m,2H),1.09-0.99(m,6H),0.82(t,J=7.3Hz,3H),0.65(t,J=7.4Hz,3H).13C NMR(126MHz,CDCl3)δ(ppm):179.06,148.08,147.30,144.86,132.78,130.09,129.38,125.44,125.24,124.84,123.47,122.57,110.95,49.25,40.55,30.00,28.12,23.20,22.87,13.95,10.26.
染料FWD10的合成:在氮气氛下,将中间体10(166.1mg,0.37mmol)、氰基乙酸(125.9mg,1.5mmol)和乙酸铵(11.4mg)溶解在甲苯(19.1mL)中,随后向混合溶液中加入冰乙酸(6.5mL),将混合物回流4小时。反应完全后,向反应物中加入水,用CH2Cl2萃取,将有机层用饱和NaCl水溶液洗涤,有机层用无水Na2SO4干燥并旋转蒸发,DCM/MeOH作洗脱剂,柱层析得到染料FWD10(黄色固体,172.3mg),收率为90.0%。
M.p:88-90℃.1H NMR(500MHz,CDCl3)δ(ppm):8.18(s,1H),7.88(br,1H),7.30(t,J=7.8Hz,4H),7.21(d,J=8.0Hz,2H),7.13(d,J=8.0Hz,4H),7.12-7.05(m,4H),6.43(br,1H),4.09(d,J=6.5Hz,2H),1.52(br,1H),1.22-0.94(m,8H),0.82(t,J=7.3Hz,3H),0.69(t,J=7.0Hz,3H).13C NMR(126MHz,CDCl3)δ(ppm):170.11,148.51,147.14,145.60,140.76,130.01,129.49,128.14,125.09,124.57,123.78,122.31,121.28,117.36,114.37,90.16,47.83,41.85,30.32,28.14,23.63,22.81,13.91,10.42.HRMS(ESI,m/z):Calcd for[M-CO2H]-C34H34N3O2 -:516.2657,found:516.2663.
实施例3
染料FHD 7的合成:
化合物12的合成:在氮气氛下,将中间体11(1.3698g,4mmol)和苯亚硒酸酐(1.7286g,4.8mmol)溶解在氯苯(30mL)中,反应回流12h。反应完全后,加入饱和NH4Cl溶液,用CH2Cl2萃取,有机相用无水Na2SO4干燥,过滤,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体13(白色固体,1.1970g),收率为80.4%。
1H NMR(300MHz,CDCl3)δ(ppm):7.83(d,J=7.2Hz,4H),7.42-7.31(m,4H),7.26-7.16(m,4H),7.04(d,J=7.5Hz,2H),6.59(d,J=8.1Hz,2H).
化合物13的合成:将中间体12(745.9mg,2.0mmol)、3,6-二溴-1,2-苯二胺(638.2mg,2.4mmol)和对甲苯磺酸(29.5mg,8mol%)加入到100mL的两口烧瓶中,在氮气氛下加入氯仿(20mL),反应回流过夜。反应完全后,加入饱和NH4Cl溶液,用CH2Cl2萃取,有机层用无水Na2SO4干燥,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体14(淡黄色粉末,1.0235mg),收率为85.0%。
1H NMR(300MHz,CDCl3)δ(ppm):8.52(d,J=8.1Hz,2H),8.03(s,2H),7.75(d,J=7.5Hz,2H),7.47(t,J=7.5Hz,2H),7.34(t,J=7.5Hz,2H),7.19-7.26(m,4H),7.34(t,J=7.5Hz,2H),6.76(d,J=7.5Hz,2H).
化合物14的合成:在100mL的两口烧瓶中加如中间体13(431.5mg,0.75mmol)和4-硼酸三苯胺(144.6mg,0.5mmol),四三苯基膦钯(34.9mg,6mol%)和碳酸钠(160.2mg,2.25mmol),在氮气氛下加入溶剂四氢呋喃(30mL)和水(6mL),将反应回流过夜。反应完全后,加入饱和NH4Cl溶液,用CH2Cl2萃取,有机相用无水Na2SO4干燥,过滤,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体14(橙色固体,210.5mg),收率为55.0%。
M.p:191-193℃.1H NMR(500MHz,CDCl3)δ(ppm):δ8.53(d,J=7.7Hz,1H),8.32(d,J=7.7Hz,1H),8.20(d,J=7.9Hz,1H),7.78(d,J=8.0Hz,1H),7.73(d,J=7.7Hz,4H),7.47(t,J=7.2Hz,1H),7.56-7.12(m,17H),7.05(q,J=7.2Hz,4H),6.78(s,2H).
化合物15的合成:在50mL的两口烧瓶中依次加入中间体14(264.6mg,0.34mmol)、1-Boc-吡咯-2-硼酸(116.6mg,0.51mmol)、四(三苯基膦)钯(26.4mg,6%mmol),碳酸钠(120.7mg,1.02mmol),在氮气保护条件下,分别加入溶剂四氢呋喃(2.4mL)和水(0.6mL),将反应体系回流过夜。反应完全后,加入饱和NH4Cl溶液,用CH2Cl2萃取,有机相用无水Na2SO4干燥,过滤,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体15(橙色固体,263.6mg),收率为90.9%。
M.p:173-175℃.1H NMR(500MHz,CDCl3)δ(ppm):8.30(d,J=7.8Hz,1H),8.23(d,J=7.7Hz,1H),7.92(s,2H),7.78(d,J=8.5Hz,2H),7.70(d,J=7.6Hz,2H),7.47(br,1H),7.37-7.23(m,8H),7.21-7.04(m,12H),7.03(t,J=7.3Hz,2H),6.79(s,2H),6.46(br,1H),6.35(t,J=3.1Hz,1H),0.89(s,9H).13C NMR(126MHz,CDCl3)δ(ppm):151.69,151.16,149.66,149.24,147.69,147.30,145.56,145.21,140.83,139.94,139.88,139.16,138.47,138.06,133.77,133.48,133.06,132.24,131.76,131.60,129.55,129.39,129.22,128.24,128.14,127.98,127.79,127.66,127.58,127.23,124.70,122.97,122.88,122.59,120.21,115.48,110.43,82.88,66.55,27.20.
化合物16的合成:在25mL的两口烧瓶中加入中间体15(266.6mg,0.31mmol),在氮气保护下,向两口瓶中加入溶剂二氯甲烷(1.8mL),在常温下搅拌使中间体15完全溶解在二氯甲烷中,随后在0℃下加入三氟乙酸(2.5ml),并在该温度下搅拌10min后,将反应转移至室温搅拌2h。反应完全后,在0℃下向反应体系中加入碳酸氢钠,使体系的pH在8~9左右,,用CH2Cl2萃取,有机相用无水Na2SO4干燥,过滤,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体16(红色固体,158.3mg),收率为67.8%。
M.p:184-187℃.1H NMR(500MHz,CDCl3)δ(ppm):12.05(s,1H),8.49(d,J=7.8Hz,1H),8.27(d,J=8.0Hz,1H),,8.17(d,J=7.5Hz,1H),7.94(d,J=8.0Hz,1H),7.79(d,J=9.0Hz,2H),7.75(d,J=7.5Hz,2H),7.41(t,J=7.3Hz,1H),7.38-7.12(m,18H),7.03(m,4H),6.93(br,1H),6.79(s,2H),6.37(dd,J=6.0,2.5Hz,1H).13C NMR(126MHz,CDCl3)δ(ppm):151.38,150.83,149.47,147.71,147.29,145.80,145.50,140.08,138.41,137.99,137.80,136.89,133.27,132.99,132.17,131.63,130.90,130.39,129.51,129.23,128.67,128.50,128.20,128.09,128.01,127.78,127.24,125.16,124.62,122.97,122.79,120.45,119.89,109.30,107.74,66.53.
化合物17的合成:在氮气氛下,将中间体16(336.2mg,0.45mmol)溶解在无水DMF(3.2ml)中。在0℃下向该溶液中加入NaH(60%的矿物油分散体,174.5mg,2.25mmol)并在相同温度下搅拌15min。逐滴加入溴代异辛烷(173.7mg,0.9mmol)并将溶液在0℃下搅拌30min。然后将反应混合物转移至室温搅拌15h后,将反应混合物加热至60℃并搅拌30min。反应完成后,加入饱和NH4Cl溶液,用CH2Cl2萃取,将有机层用无水Na2SO4干燥并旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体17(橙色固体,311.0mg),收率为79.8%。
M.p:103-105℃.1H NMR(500MHz,CDCl3)δ(ppm):8.34(d,J=7.5Hz,1H),8.24(d,J=7.5Hz,1H),7.95(d,J=7.5Hz,1H),7.89(d,J=7.5Hz,1H),7.81(d,J=8.5Hz,2H),7.73(t,J=6Hz,2H),7.39-7.24(m,8H),7.24-7.10(m,10H),7.08-6.98(m,4H),6.84(br,1H),6.79(d,J=27Hz,2H),6.40(br,1H),6.31(t,J=3.0Hz,1H),3.83-3.73(m,2H),1.46(m,1H),1.08-0.91(m,8H),0.66(t,J=7.3Hz,3H),0.51(t,J=7.3Hz,3H).13C NMR(126MHz,CDCl3)δ(ppm):151.72,151.53,149.71,147.69,147.40,145.39,145.16,140.57,140.09,140.04,139.63,139.41,138.28,138.07,133.62,132.55,132.15,131.84,131.67,131.33,129.54,129.24,128.25,128.18,127.85,127.69,127.62,127.03,124.68,123.00,122.69,120.35,111.23,107.48,66.59,51.96,41.14,30.49,28.44,23.78,22.70,13.93,10.46.
化合物18的合成:在氮气氛下,将中间体17(200.2mg,0.23mmol)溶解在无水氯仿(1.4mL)中,在0℃下,逐滴向该溶液中分别加入N,N-二甲基甲酰胺(81.9mg)和POCl 3(98mg)。将混合物在0℃下搅拌30min,然后升温至室温,在室温下搅拌30min,最后回流30min。冷却后,向该溶液中加入乙酸钠(113.2mg,1.38mmol)的水溶液(1.4mL)并在80℃下搅拌15min。冷却后,向反应混合物中加入水和CH2Cl2。分离有机层,水层,用CH2Cl2萃取,将有机层用饱和NaHCO3水溶液洗涤,用无水Na2SO4干燥,旋转蒸发,PE/DCM作洗脱剂,柱层析得到中间体18(橙色固体,122.7mg),收率为60.3%。
M.p:132-134℃.1H NMR(500MHz,CDCl3)δ(ppm):9.60(s,1H),8.34(d,J=7.1Hz,1H),8.17(d,J=7.6Hz,1H),7.99(d,J=7.6Hz,1H),7.91(d,J=7.6Hz,1H),7.81(d,J=8.7Hz,2H),7.72(d,J=7.6Hz,2H),7.37-7.24(m,8H),7.24-7.11(m,10H),7.09(d,J=4.0Hz,1H),7.08-6.98(m,4H),6.76(s,2H),6.49(d,J=4.0Hz,1H),4.33(d,J=6.6Hz,2H),1.58(m,1H),1.08-0.93(m,8H),0.63(t,J=7.1Hz,3H),0.49(t,J=7.4Hz,3H).13C NMR(126MHz,CDCl3)δ(ppm):179.21,152.44,152.17,149.57,147.77,147.57,145.55,145.28,141.53,141.32,140.32,140.06,139.26,138.00,137.68,133.65,133.54,132.84,132.14,131.71,131.45,130.08,129.58,129.48,129.28,129.07,128.36,128.29,127.91,127.84,127.65,127.01,124.81,123.18,122.47,120.42,113.53,66.54,50.43,40.84,30.18,28.27,23.43,22.73,13.89,10.40.
染料FHD 7的合成:在氮气氛下,将中间体18(119.8mg,0.13mmol)、氰基乙酸(36.5mg,0.39mmol)和乙酸铵(10.2mg)溶解在甲苯(6.7mL)中,随后向混合溶液中加入冰乙酸(2.3ml),将混合物回流4小时。反应完全后,向反应物中加入水,用CH2Cl2萃取,将有机层用饱和NaCl溶液洗涤,有机层用无水Na2SO4干燥并旋转蒸发,DCM/MeOH作洗脱剂,柱层析得到染料FHD 7(红色固体,105.6mg),收率为84.7%。
M.p:196-198℃.1H NMR(500MHz,CDCl3)δ(ppm):8.36(d,J=7.5Hz,1H),8.19(s,1H),8.06(d,J=7.5Hz,1H),8.00(d,J=7.0Hz,2H),7.90(d,J=7.0Hz,1H),7.81(d,J=8.5Hz,2H),7.73(d,J=7.0Hz,2H),7.38–7.24(m,8H),7.24-7.11(m,10H),7.09-6.97(m,4H),6.76(s,2H),6.67(d,J=3.5Hz,1H),3.98(br,2H),1.49(br,1H),1.05–0.80(m,8H),0.63(br,3H),0.51(d,J=6.5Hz,3H).13C NMR(126MHz,CDCl3)δ(ppm):169.92,152.96,152.69,149.81,148.21,147.82,145.88,145.61,142.74,142.09,141.22,140.41,139.61,138.15,137.87,133.91,133.81,132.47,132.02,131.47,130.00,129.89,129.60,129.42,128.70,128.64,128.49,128.26,128.00,127.87,127.24,125.16,123.56,122.67,121.23,120.79,117.53,116.90,66.83,49.31,42.41,30.77,28.54,24.09,22.91,14.10,10.76.HRMS(ESI/Q-TOF,m/z):Calcd for C67H53N5O2:959.4199,found:959.4195.
FWD10,FWD9,FHD7染料的光电性能
在模拟AM 1.5太阳光照射下,基于染料FWD9,FWD10和FHD7的DSSCs的电流密度-电压(J-V)曲线如图1所示,以及短路电流密度(Jsc)、开路电压(Voc)等参数总结在表1中。
表1染料FWD9、FWD10和FHD7制作的DSSCs的光伏性能参数
从表1可以看出,基于染料FWD9,FWD10和FHD7的DSSCs的电流短路密度(Jsc)分别为6.10mA/cm2,6.67mA/cm2和6.83mA/cm2,开路电压(Voc)则分别为0.64V,0.69V和0.64V,填充因子(FF)为0.74、0.76、0.73。通过计算得到这三种染料的光电转换效率分别为2.90%、3.52%、3.20%,其中由于染料FWD9具有适中的开路电压和最低的短路电流密度,因此基于该染料的电池具有最低的光电转换效率,染料FWD10具有最高的开路电压和适中的短路电流密度,因此它的转换效率最高。
当染料吸附在TiO2薄膜上时,由于两者之间的非共价键作用,可能导致染料在半导体表面上形成聚集体。为了减少染料分子的聚集,通常在染料中添加共吸附剂来改善电池的光伏性能。共吸附剂主要有以下两个作用:1)减少染料的聚集,提高电子注入效率;2)染料与共吸附剂形成的绝缘层有效的抑制了电子复合。但吸附剂的引入在一定程度上会降低染料在TiO2薄膜的吸附量,从而降低电池的光伏性能。本发明通过在染料中添加共吸附剂去氧胆酸(CDCA),来研究在CDCA存在下DSSCs的性能。从图1中的J-V曲线和表1中的相关数据可以发现,在添加CDCA之后,基于FWD9,FWD10和FHD7的DSSCs的开路电压变化不大,但电池的电流短路密度均减小,其中基于染料FHD7的DSSCs的电流短路密度比不添加CDCA时将近减小了一半。在添加CDCA(3mM)之后,由于短路电流密度在不同程度上降低,使基于FWD9、FWD10、FHD7这三种染料的DSSCs的光电转换效率分别降低了21.0%,27.3%和42.8%。显着降低的光电转换效率表明这三种染料可以有效的抑制染料分子间聚集,主要是因为烷基吡咯作为共轭π-桥时,在氮原子上引入的额外疏水烷基链可以有效地阻止电极中注入的电子与电解质中的之间的电子复合,并且引入的烷基链与共轭平面之间呈一定角度,这有利于抑制由于共轭体系之间的相互作用而产生染料分子的分子间聚集,加入CDCA后染料的吸附量减少,光电转换效率降低。
综上所述,本发明的FWD9,FWD10和FHD7染料相比于传统的金属配位染料,展现出更好的摩尔消光系数、短路光电流密度和光电转换效率,从而极大的增强了太阳能电池的效率。此外,带有支链的烷基吡咯,有助于抑制聚集,从而提高效率在制造高效染料敏化太阳能电池中具有良好的应用前景。
Claims (10)
1.三苯胺类有机染料,化学结构通式如式(1)所示:式中,R1选自氢基或苯已烯基,R2选自氢基或苯已烯基,为喹喔啉衍生物。
2.根据权利要求1所述的三苯胺类有机染料,其特征在于,所述的三苯胺类有机染料为
3.根据权利要求1或2所述的三苯胺类有机染料的合成方法,其特征在于,具体步骤如下:
步骤1,氮气保护下,以四(三苯基膦)钯为催化剂,在四氢呋喃存在下,将化合物A和1-Boc-吡咯-2-硼酸和水混合,回流反应,经Suzuki偶联反应制备化合物B,所述的化合物A选自合成路线如下:
步骤2,氮气保护下,在四氢呋喃存在下,在化合物B中加入甲醇钠和甲醇,经水解反应制备化合物C,合成路线如下:
步骤3,在DMF存在下,化合物C和溴代异辛烷发生取代反应制备D,合成路线如下:
步骤4,氮气保护下,在DMF存在下,将化合物D和POCl3混合,回流经Vilsmeier-Haak反应制备E,合成路线如下:
步骤5,在氮气保护下,在氯仿存在下,将化合物E和氢乙酸混合,回流经Knoevenagel缩合反应制备目标化合物三苯胺类有机染料,合成路线如下:
4.根据权利要求3所述的合成方法,其特征在于,步骤1中,所述的化合物A与1-Boc-吡咯-2-硼酸以及碳酸钠的摩尔比为1:2.2:3;所述的催化剂四(三苯基膦)钯的物质的量是化合物A的6%;所述的回流反应温度为60~80℃,所述的回流反应时间为12h以上。
5.根据权利要求3所述的合成方法,其特征在于,步骤2中,所述的化合物B与甲醇钠的摩尔比为1:4;所述的水解反应时间为2h以上。
6.根据权利要求3所述的合成方法,其特征在于,步骤3中,所述的化合物C与溴代异辛烷和NaH摩尔比为1:2.2:5;所述的反应时间为2h以上。
7.根据权利要求3所述的合成方法,其特征在于,步骤4中,所述的化合物D与N,N-二甲基甲酰胺以及POCl3的物质的量比为2:1:3.7;所述的反应时间为2h以上。
8.根据权利要求3所述的合成方法,其特征在于,步骤5中,所述的化合物E与氰基乙酸摩尔比为1:3.9;所述的反应时间为4h以上。
9.根据权利要求3所述的合成方法,其特征在于,步骤5中,目标产物通过以下步骤进行后处理:反应完全后,向反应物中加入水,用CH2Cl2萃取,有机相用饱和NaCl溶液洗涤,有机层用无水Na2SO4干燥并旋转蒸发,DCM/MeOH作洗脱剂,柱层析得到有机染料。
10.根据权利要求1或2所述的三苯胺类有机染料在制备染料敏化太阳能电池中的应用。
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