CN101935462A - 一种双咔唑基染料及其制法和应用 - Google Patents
一种双咔唑基染料及其制法和应用 Download PDFInfo
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- 239000000975 dye Substances 0.000 claims abstract description 69
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
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- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 2
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- SZPAKLWKGFHLKV-UHFFFAOYSA-N C(C)(=O)O.CC=1C(=O)CC(CC1C)(C)C.N#CC#N.N#CC#N Chemical compound C(C)(=O)O.CC=1C(=O)CC(CC1C)(C)C.N#CC#N.N#CC#N SZPAKLWKGFHLKV-UHFFFAOYSA-N 0.000 description 1
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- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
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Abstract
本发明公开了一种双咔唑基染料及其制法和应用,属于精细化工中的光电转化材料应用领域。本发明将双咔唑及其衍生物单元通过烷基连接形成双电子给体,在此基础上分别用双键延伸共轭π桥,末端接上氰基乙酸作为电子受体,应用该方法合成了一系列染料。由于双咔唑基染料具有与TiO2更强的结合能力,并且有效地防止染料在TiO2表面的聚集,使得其在相同条件下具有比单咔唑基染料更优越的性能。而且双咔唑基染料的合成方法简单,原料易得,可代替价格昂贵、制备提纯较难的贵金属光敏染料,有效地降低染料敏化太阳能电池成本。
Description
技术领域
本发明公开了一种双咔唑基染料及其制法和应用,属于精细化工中的光电转化材料应用领域,具体涉及一类双咔唑基染料及其衍生物的设计、合成,以及所述染料在染料敏化太阳能电池方面的应用。
技术背景
染料敏化太阳能电池(DSSCs)是1991年瑞士科学家M.首次提出并设计的一种新型的将太阳能转化为电能的装置。其构成一般由以下几方面组成:以镀Pt的导电玻璃为基板的光阴极,吸附了光敏染料的纳米多孔氧化物薄膜和透明导电基板组成的光阳极,填充在两电极之间的电解质以及密封材料。这类电池与传统的硅基太阳能电池相比具有结构简单、制作成本低等优点,而且其光电转化效率目前已达11%以上,是一类具有广泛应用前景的光电转换装置。光敏染料是染料敏化太阳能电池中非常重要的组成部分,染料的结构设计对于这类电池至关重要。目前,光电转化效率最高的依然是钌多吡啶配合物。然而钌属于稀有贵金属,相应的钌多吡啶配合物的分离提纯也有相当的难度,这限制了DSSCs成本的降低和未来的大规模实用化。为此,不含金属的有机光敏染料近年来在DSSCs中得到广泛的应用。同钉多吡啶配合物染料(如N3,N719等)相比,有机光敏染料具有结构多样、制备提纯相对容易、摩尔消光系数高等诸多优点。近年来品种多样的有机光敏染料发展迅速,为了进一步降低染料敏化太阳能电池成本,本发明设计合成了一类新型的咔唑类有机光敏染料。
发明内容
本发明的目的是合成一类新型的不含金属纯有机光敏染料,这类染料是以双咔唑及其衍生物为共轭体系,通过烷基链将双咔唑单元连接起来,在此基础上分别延伸共轭π桥,在末端接上氰基乙酸,用来吸附在TiO2上,组成一类双链电子推拉型染料。这类染料在染料敏化太阳能电池上具有很好的应用性能。
本发明提供了一类新型的咔唑光敏染料,这类染料具有如下结构:
其中:R1~R6为氢、C1~C20的直链烷基、C1~C20的支链烷基、C1~C20的酰胺基、C1~C20烷氧基或卤素;m为1~6的自然数;X为氢、C1~C20的直链烷基、C1~C20的支链烷基、C1~C20的酰胺基、C1~C20烷氧基、卤素或
其中,X1~X5为氢,C1~C20的直链烷基,C1~C20的支链烷基,C1~C20的酰胺基,C1~C20烷氧基或卤素;X6,X7为氢,C1~C20的直链烷基,C1~C20的支链烷基或C1~C20烷氧基;X8,X9为氢,C1~C20的直链烷基或C1~C20的支链烷基;Y为C4~C20的直链烷基,C4~C20的支链烷基或
其中,Y1~Y4为氢,C1~C20的直链烷基,C1~C20的支链烷基,C1~C20的酰胺基,C1~C20烷氧基或卤素;W为氮,氧或硫。
所述的一种双咔唑基染料的制备方法,包括以下步骤:
反应均在惰性气氛中进行;
(1)将碱和A按照摩尔比1~5∶1混合,在0~40℃下搅拌1~60min;然后滴加B,B与A的摩尔比为1∶2~3∶2,反应1~48h;加入到冰水混合物中搅拌10~30min,过滤,将固体溶于二氯甲烷中,水洗,分液,干燥有机相,重结晶后得到化合物M1;
(2)向冰浴中的N,N-二甲基甲酰胺缓慢滴加POCl3,N,N-二甲基甲酰胺与POCl3的摩尔比为1~5∶1,恢复室温,搅拌1~2h;然后滴加溶于溶剂的M1,M1与POCl3的摩尔比为1∶8~1∶1,在50~120℃下搅拌1~24h;调节pH为6~7,搅拌1~10h,加入二氯甲烷萃取,有机相水洗,干燥,浓缩,得到化合物M2;
(3)将M2和氰基乙酸按摩尔比为1∶20~1∶2加入到溶剂中,滴加4~10滴有机碱,在50~120℃下搅拌1~24h;调节pH为1~5,搅拌1~60min,过滤,固体干燥后进行柱层析分离得到化合物M3;
所述化合物A为:
所述化合物B为Br-Y-Br;
所述化合物M1为:
所述化合物M2为:
所述化合物M3为:
其中:R1~R6为氢、C1~C20的直链烷基、C1~C20的支链烷基、C1~C20的酰胺基、C1~C20烷氧基或卤素;m为1~6的自然数;X为氢、C1~C20的直链烷基、C1~C20的支链烷基、C1~C20的酰胺基、C1~C20烷氧基、卤素或
X1~X5为氢,C1~C20的直链烷基,C1~C20的支链烷基,C1~C20的酰胺基,C1~C20烷氧基或卤素;X6,X7为氢,C1~C20的直链烷基,C1~C20的支链烷基或C1~C20烷氧基;X8,X9为氢,C1~C20的直链烷基或C1~C20的支链烷基;
其中,
Y为C4~C20的直链烷基,C4~C20的支链烷基或
Y1~Y4为氢,C1~C20的直链烷基,C1~C20的支链烷基,C1~C20的酰胺基,C1~C20烷氧基或卤素;W为氮、氧或硫。
所述碱为氢氧化钠或氢氧化钾。
步骤(1)所述溶剂为二甲基亚砜或N,N-二甲基甲酰胺。
步骤(2)所述溶剂为氯仿、二氯甲烷或1,2-二氯乙烷。
步骤(3)所述溶剂为氯仿、乙腈或醋酸。
所述有机碱为吡啶、哌啶或三乙胺。
所述的一种双咔唑基染料在染料敏化太阳能电池中的应用。
本发明咔唑染料的合成方法简单,原料价廉易得,其合成按如下反应式进行:
当m=1时的反应式:
本发明合成的咔唑染料在染料料敏化太阳能电池中的应用,包括染料敏化太阳能电池的组成和构造、制备步骤和电池性能测试为:
(1)染料敏化太阳能电池的组成和构造:染料敏化太阳能电池主要由光阳极、光阴极及它们的基板(导电玻璃)和电解质组成;光阳极基板工作区域一侧导电玻璃中间设有纳米多孔TiO2薄膜,并浸染有咔唑染料;光阴极基板工作区域一侧电玻璃中间设有催化剂(Pt)层;光阳极和光阴极相对间隔设置,中间纳米多孔TiO2薄膜周边用密封材料密封形成密闭的腔体,腔体内填充有电解质;
(2)所述染料敏化太阳能电池的制备步骤如下:
(a)导电玻璃的预处理:将导电玻璃依次在去油剂、无水乙醇和去离子水中用超声波清洗,然后烘干备用;
(b)TiO2浆料的制备:将2g P25型二氧化钛纳米颗粒分散在4ml去离子水与0.1ml乙酰丙酮的混合溶剂中,加入两滴Triton X-100;
(c)染料溶液的配制:将权利要求1所述的咔唑染料溶于四氢呋喃中,配制成5×10-4mol·L-1溶液;
(d)电解质溶液的配制:用绝对干燥的乙腈配制含有0.6M四丁基碘化铵,0.1M LiI,0.05M I2和0.5M对叔丁基吡啶的溶液;
(e)光阳极的制备:在步骤(1)处理好的导电玻璃上,通过丝网印刷制备底面积为0.237cm2,厚度为15~20μm的圆柱形纳米多孔TiO2薄膜材料,并在450℃下保持30分钟后缓慢降至室温,再将其浸于40mM TiCl4水溶液中,在70℃保持半小时,取出后用去离子水冲洗干净,在500℃烘焙半小时;
(f)光阳极的敏化:将步骤(5)制备的光阳极纳米多孔TiO2薄膜层浸染在权利要求1所述的咔唑染料按步骤(3)配制后的溶液中,染浴12~24h;
(g)光阴极的制备:在经过预处理的光阴极基板上,通过热分解法镀上Pt做催化剂层,然后钻针头大小孔备用;
(h)电池的封装:在光阳极TiO2薄膜的周边位置,放上经用磨具分割成内圆回字形的Surlyn1702热熔膜,盖上光阴极,然后在100℃加热2分钟密封;
(i)将上述电解质通过真空或者手工方法从光阴极的小孔注入,待两个电极之间没有气泡后,将其密封,制得染料敏化太阳能电池;
(3)电池性能测试:从电池的光阳极和光阴极分别引出导线,接到电池性能测试装置上,电池的工作面积为0.237cm2,用太阳光模拟器模拟太阳光,将光强度调节至100mW/cm2测得的光电转化效率为0.23~2.18%,短路电流为0.87-3.24mA/cm2,开路电压为0.512~0.717V,填充因子为0.60-0.70。
本发明相对于现有技术所具有的优点及有益效果如下:
咔唑是一种富电子的含氮杂环化合物,以其为电子给体的染料被广泛用于染料敏化太阳能电池的研究,其中最高光电转化效率达7.7%。
本发明设计并合成一类基于双咔唑及其衍生物为电子给体、双氰基乙酸为受体的新型染料。该染料具有结构简单,合成容易,防止止染料分子间堆积,光电转化性能良好等优点。
附图说明
图1为染料敏化太阳能电池封装俯视图,
图2为染料敏化太阳能电池封装侧视图;
其中:101导电玻璃
102镀铂的导电玻璃
103吸附了光敏染料的纳米TiO2膜
104热固性密封圈
105电解液注入小孔
图3为实施例1及实施例2中所合成的染料在四氢呋喃溶剂中(浓度2×10-5M)紫外/可见吸收谱图。横坐标表示的是吸收波长,单位为纳米,纵坐标表示的是吸光强度,单位为1。
图4为实施例1及实施例2中所合成的染料在四氢呋喃溶剂中(浓度2×10-5M)的荧光发射谱图。横坐标表示的是发射波长,单位为纳米,纵坐标表示的是发射强度,单位为1。
图5和图6为染料敏化太阳能电池的放电曲线图。
横坐标表示的是电压,单位为伏;纵坐标表示的是电流密度,单位为毫安每平方厘米。其中:图5为用Solaronix公司提供的N719光敏染料,并按照实施例4所述方法组装的电池测得的放电曲线图,图6为利用实施例1及实施例2中合成的光敏染料,并按照实施例4所述方法组装的电池测得的电池放电曲线图。
具体实施方式
下面结合实施例对本发明做进一步地详细说明,但是本发明要求保护的范围并不局限于实施例表示的范围。
实施例1
1,6-双-(3-氰基丙烯酸基咔唑)正己烷的合成
反应均在氮气保护下的干燥环境中进行
(1)1,6-双咔唑正己烷的合成
将1.67g(10mmol)的咔唑溶于15ml DMSO中,加入2.24g(40mmol)KOH,在室温搅拌20min。然后滴加1.22g(5mmol)的1,6-二溴己烷,继续反应48h。倒入冰水混合物中剧烈搅拌30min,过滤,固体溶解于二氯甲烷中,水洗3次,干燥有机相,重结晶得到1.42g(3.41mmol)产物,收率为68%。熔点:126-127℃。
(2)1,6-双-(3-甲酰基咔唑)正己烷的合成
向冰浴中的1~20份731mg(10mmol)DMF中加入1.23g(8mmol)POCl3,然后撤去冰浴,恢复至室温,搅拌反应1h。然后缓慢滴加416mg(1mmol)溶于15ml 1,2-二氯乙烷中的1,6-双咔唑正己烷,在85℃下反应24h。反应结束后冷却,滴加2M的NaOH溶液调节pH≈6,搅拌2h,分液,再用二氯甲烷萃取3次,合并有机层,有机相水洗3次,干燥,浓缩,粗产物通过柱层析分离提纯,得到363mg(0.77mmol)产物,收率为77%。熔点:158-160℃。
(3)1,6-双-(3-氰基丙烯酸基咔唑)正己烷的合成
将236mg(0.5mmol)1,6-双-(3-甲酰基咔唑)正己烷加入到三口瓶中,以15ml氯仿作为溶剂,加入425mg(5mmol)氰基乙酸,滴加8滴哌啶,在75℃下搅拌反应8h。反应结束后冷却,滴加0.1M的盐酸,调节pH≈3,搅拌30min,过滤,固体干燥后进行柱层析分离得到243mg(0.40mmol)产物,收率为80%。核磁1H-NMR(400MHz,CDCl3)(δ/ppm):1.18(4H,m),1.62(4H,m),4.28(4H,t),7.22(2H,t),7.44(2H,t),7.54(2H,d,J=8Hz),7.65(2H,d,J=8Hz),8.05(2H,d,J=8Hz),8.15(2H,dd,J1=1.2Hz,J2=1.2Hz),8.31(2H,s),8.70(2H,s).质谱ESI-MS:Found m/z 605.7([M-H]-).ELEM.ANAL.Calc.For C38H30N4O4:C,75.23;H,4.98;N,9.24.Found:C,75.21;H,4.99;N,9.23.
实施例2
3-(9-乙基咔唑)-2-氰基丙烯酸的合成
反应均在氮气保护下的干燥环境中进行
(1)9-乙基咔唑的合成
将1.67g(10mmol)的咔唑溶于15ml DMSO中,加入2.24g(40mmol)KOH,在室温下搅拌20min。然后滴加1.64g(15mmol)的溴乙烷,继续反应48h。倒入冰水混合物中搅拌10min,过滤,固体溶解于二氯甲烷中,水洗3次,干燥有机相,重结晶得到1.40g(7.2mmol)产物,收率为72%。熔点:70-72℃。
(2)9-乙基-3-甲酰基咔唑的合成
在冰浴中1~20份的731mg(10mmol)DMF中加入1.23g(8mmol)POCl,然后撤去冰浴,恢复至室温,搅拌反应1h。然后缓慢滴加390mg(2mmol)溶于15ml 1,2-二氯乙烷中的9-乙基咔唑,在85℃下反应24h。反应结束后冷却,滴加2M的NaOH溶液调节pH≈6,搅拌2h,分液,再用二氯甲烷萃取3次,合并有机层,有机相水洗3次,干燥,浓缩,粗产物通过柱层析分离提纯,得到330mg(1.48mmol)产物,收率为74%。熔点:88-89℃。
(3)3-(9-乙基咔唑)-2-氰基丙烯酸的合成
将223mg(1mmol)9-乙基-3-甲酰基咔唑加入到三口瓶中,以15ml氯仿作为溶剂,加入425mg(5mmol)氰基乙酸,滴加8滴哌啶,在75℃下搅拌反应8h。反应结束后冷却,滴加0.1M的盐酸,调节pH≈3,搅拌30min,过滤,固体干燥后进行柱层析分离得到246mg(0.85mmol)产物,收率为85%。核磁1H-NMR(400MHz,CDCl3)(δ/ppm):1.33(3H,t),4.5(2H,m),7.31(1H,t),7.55(1H,t),7.71(1H,d,J=8Hz),7.83(1H,d,J=8Hz),8.15(1H,d,J=8Hz),8.29(1H,dd,J1=1.2Hz,J2=1.2Hz),8.45(1H,s),8.85(1H,s).质谱ESI-MS:Found m/z 289.2([M-H]-).ELEM.ANAL.Calc.For C38H30N4O4S2:C,74.47;H,4.86;N,9.65.Found:C,47.45;H,4.88;N,9.54.
实施例3
对实施例1及实施例2染料的紫外-可见吸收光谱/荧光光谱测试,紫外-可见吸收光谱和荧光发射谱图分别为图3、图4所示。
溶剂:四氢呋喃
浓度:2×10-5M
温度:室温
仪器:Shimadzu UV-2450紫外可见风光光度计,Hitachi F-4500荧光光谱仪
表1实施例1和2中染料的最大紫外/可见吸收波长和最大荧光发射波长(nm)数据比较,将所得的数据汇总于表1中
表1
染料 | 最大紫外/可见光吸收波长(nm) | 最大荧光发射波长(nm) |
实施例1 | 387 | 460 |
实施例2 | 387 | 452 |
实施例4
本发明中染料敏化太阳能电池如图1和2的制作如下:
(1)导电玻璃(FTO)的预处理:将导电玻璃依次在去油剂、无水乙醇和去离子水中用超声波充分清洗,然后烘干备用;
(2)TiO2浆料的制备:将2g P25二氧化钛纳米颗粒分散在4ml去离子水和0.1ml的乙酰丙酮混合溶剂中,分散结束后加入两滴Triton X-100;
(3)染料溶液的配制:将实施例1制的的咔唑染料溶于四氢呋喃中,配制成2×10-4mol·L-1溶液;
(4)电解质溶液的配制:用绝对干燥的乙腈配制含有0.6M四丁基碘化铵,0.1M LiI,0.05M I2和0.5M对叔丁基吡啶的溶液;
(5)光阳极的制备:在步骤(1)处理好的导电玻璃上,通过丝网印刷制备底面积为0.237cm2,厚度为15~20μm的圆柱形纳米多孔TiO2薄膜材料,并在450℃下保持30分钟后缓慢降至室温,再将其浸于40mM TiCl4水溶液中,在70℃保持半小时,取出后用去离子水冲洗干净,在500℃烘焙半小时;
(6)光阳极的敏化:将步骤(5)制备的光阳极纳米多孔TiO2薄膜层浸染在实施例1的咔唑染料按步骤(3)配制后的溶液中,染浴12~24h;
(7)光阴极的制备:在经过预处理的光阴极基板上,通过热分解法镀上Pt做催化剂层,然后钻针头大小孔备用;
(8)电池的封装:在光阳极纳米多孔TiO2薄膜的周边位置,放上经用磨具分割成内圆回字形的Surlyn1702热熔膜,上面盖上光阴极,然后通过100℃加热2分钟进行密封;
(9)将上述电解质通过真空或者手工方法从光阴极的小孔注入,待两个电极之间没有气泡后,将小孔密封,制得染料敏化太阳能电池供测试使用;
实施例5
染料敏化太阳能电池性能测试:
将按照实施例4中的电池制备步骤,以N719为敏化染料组装成电池,分别从光阳极和光阴极引出导线,接到电池性能测试装置上,电池的有效工作面积为0.237cm2时,用太阳光模拟器模拟太阳光,将光强度调节至100mW/cm2测得的光电转化效率为5.82%,短路电流为12.61mA/cm2,开路电压为0.734V,填充因子为0.624;测得的电池放电曲线如图5所示。
将按照实施例4中的电池制备步骤,分别以实施例1和实施例2合成的染料组装成电池,分别从光阳极和光阴极引出导线,接到电池性能测试装置上,电池的工作面积为0.237cm2时,用太阳光模拟器模拟太阳光,将光强度调节至100mW/cm2分别测其光电转化效率。图6为利用实施例1及实施例2中合成的光敏染料,并按照实施例4所述方法组装的电池测得的电池放电曲线图。N719、实施例1和实施例2染料用于染料敏化太阳能电池性能数据对比,将所测数据汇总于表2。
表2
Claims (8)
1.一种双咔唑基染料,其特征在于,具有以下结构通式:
其中:R1~R6为氢、C1~C20的直链烷基、C1~C20的支链烷基、C1~C20的酰胺基、C1~C20烷氧基或卤素;m为1~6的自然数;X为氢、C1~C20的直链烷基、C1~C20的支链烷基、C1~C20的酰胺基、C1~C20烷氧基、卤素或
其中,X1~X5为氢,C1~C20的直链烷基C1~C20的支链烷基,C1~C20的酰胺基,C1~C20烷氧基或卤素;X6,X7为氢,C1~C20的直链烷基,C1~C20的支链烷基或C1~C20烷氧基;X8,X9为氢,C1~C20的直链烷基或C1~C20的支链烷基;Y为C4~C20的直链烷基,C4~C20的支链烷基或
其中,Y1~Y4为氢,C1~C20的直链烷基,C1~C20的支链烷基,C1~C20的酰胺基,C1~C20烷氧基或卤素;W为氮,氧或硫。
2.权利要求1所述的一种双咔唑基染料的制备方法,其特征在于,包括以下步骤:
反应均在惰性气氛中进行;
(1)将碱和A按照摩尔比1~5∶1混合,在0~40℃下搅拌1~60min;然后滴加B,B与A的摩尔比为1∶2~3∶2,反应1~48h;加入到冰水混合物中搅拌10~30min,过滤,将固体溶于二氯甲烷中,水洗,分液,干燥有机相,重结晶后得到化合物M1;
(2)向冰浴中的N,N-二甲基甲酰胺缓慢滴加POCl3,N,N-二甲基甲酰胺与POCl3的摩尔比为1~5∶1,恢复室温,搅拌1~2h;然后滴加溶于溶剂的M1,M1与POCl3的摩尔比为1∶8~1∶1,在50~120℃下搅拌1~24h;调节pH为6~7,搅拌1~10h,加入二氯甲烷萃取,有机相水洗,干燥,浓缩,得到化合物M2;
(3)将M2和氰基乙酸按摩尔比为1∶20~1∶2加入到溶剂中,滴加4~10滴有机碱,在50~120℃下搅拌1~24h;调节pH为1~5,搅拌1~60min,过滤,固体干燥后进行柱层析分离得到化合物M3;
所述化合物A为:
所述化合物B为Br-Y-Br;
所述化合物M1为:
所述化合物M2为:
所述化合物M3为:
其中:R1~R6为氢、C1~C20的直链烷基、C1~C20的支链烷基、C1~C20的酰胺基、C1~C20烷氧基或卤素;m为1~6的自然数;X为氢、C1~C20的直链烷基、C1~C20的支链烷基、C1~C20的酰胺基、C1~C20烷氧基、卤素或
X1~X5为氢,C1~C20的直链烷基,C1~C20的支链烷基,C1~C20的酰胺基,C1~C20烷氧基或卤素;X6,X7为氢,C1~C20的直链烷基,C1~C20的支链烷基或C1~C20烷氧基;X8,X9为氢,C1~C20的直链烷基或C1~C20的支链烷基;
其中,
Y为C4~C20的直链烷基,C4~C20的支链烷基或
Y1~Y4为氢,C1~C20的直链烷基,C1~C20的支链烷基,C1~C20的酰胺基,C1~C20烷氧基或卤素;W为氮,氧或硫。
3.根据权利要求2所述的制备方法,其特征在于,所述碱为氢氧化钠或氢氧化钾。
4.根据权利要求2所述的制备方法,其特征在于,所述有机碱为吡啶、哌啶或三乙胺。
5.根据权利要求2-4之一所述的制备方法,其特征在于,步骤(1)所述溶剂为二甲基亚砜或N,N-二甲基甲酰胺。
6.根据权利要求2-4之一所述的制备方法,其特征在于,步骤(2)所述溶剂为氯仿、二氯甲烷或1,2-二氯乙烷。
7.根据权利要求2-4之一所述的制备方法,其特征在于,步骤(3)所述溶剂为氯仿、乙腈或醋酸。
8.权利要求1所述的一种双咔唑基染料在染料敏化太阳能电池中的应用。
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CN116217559A (zh) * | 2022-12-29 | 2023-06-06 | 浙江工业大学 | 一种带天线的咔唑类化合物及其制备方法和应用 |
CN116217559B (zh) * | 2022-12-29 | 2024-04-02 | 浙江工业大学 | 一种带天线的咔唑类化合物及其制备方法和应用 |
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