CN110759899A - 一种高刚性喹喔啉类染料敏化剂及在制备方法和应用 - Google Patents
一种高刚性喹喔啉类染料敏化剂及在制备方法和应用 Download PDFInfo
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- CN110759899A CN110759899A CN201910574655.2A CN201910574655A CN110759899A CN 110759899 A CN110759899 A CN 110759899A CN 201910574655 A CN201910574655 A CN 201910574655A CN 110759899 A CN110759899 A CN 110759899A
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- 238000005859 coupling reaction Methods 0.000 claims description 9
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了一种以喹喔啉为辅助受体的染料敏化剂及其三组分一锅法制备和在染料敏化太阳能电池中的应用，该染料敏化剂的结构如通式(1)所示。该化合物基于ICT电子转移机理，作为发电层材料应用于太阳能电池器件，本发明制作的器件具有良好的光电性能，能够满足太阳能电池制造企业的要求。
Description
技术领域
本发明涉及太阳能发电技术领域，尤其是涉及一种以喹喔啉为辅助受体的具有高刚性结构的染料敏化剂及其作为光电转换材料在染料敏化太阳能电池器件上的应用。
背景技术
在所有可获得的能源中，太阳能是最清洁、最廉价和最丰富的可持续能源。自1991年O’regan和Gratzel报道了第一种用于光伏器件的钌敏化剂后，DSSCs因其转换效率高、制造工艺简单、制造成本低而吸引广泛的研究兴趣。在过去的几十年中，在模拟的1.5global(AM 1.5g)条件下，DSSCs的功率转换效率(PCE)从7％稳步提高到14.3％。DSSCs的电极、半导体、电解质、敏化剂等各组分对光伏性能均有显著影响。研究表明，固液电解质能显著提高DSSCs的热稳定性和长期稳定性。特别是增敏剂在改善DSSCs中PCE的过程中起着至关重要的作用。因此，为了在保持高电荷复合电阻的同时获得更多的光子，对染料敏化剂进行了大量的研究。在DSSCs中，钌染料历来作为染料敏化剂使用，但由于成本较高、毒性高、稀缺性较差，对其未来的应用有一定的危害。卟啉染料是钌基敏化剂的替代品之一，在CoII/CoIII电解液下以锌卟啉为敏化剂，其效率也达到13％。然而，锌卟啉增敏剂的合成工艺复杂，纯化困难，DSSCs长期稳定性差。
近年来，有机染料敏化剂因其独特的优点受到了人们的广泛关注，与金属络合物染料敏化剂相比，有机染料敏化剂具有分子设计方便、可调谐吸收、生态友好、无资源限制、合成纯化成本低等优点。一般来说,不含金属的染料敏化剂采用主流化donor-π-bridge-acceptor架构是非常可取的,使有效电荷转移。推挽式体系结构可以产生一个分子内电荷转移(ICT)π-bridge供体和受体之间,表现出优良的带隙调优和有利的吸收光谱。基于吲哚、吩噻嗪、香豆素、三苯基胺和吲哚林的各种无金属有机敏化剂已被探索，以达到更好的太阳能发电效率。到目前为止，制备的DSSCs无金属有机敏化剂的效率已经达到了令人鼓舞的13.0％以上。
近年来，喹喔啉类敏化剂得到了积极的研究，光伏性能得到了显著的改善。最近,田课题组报道新的quinoxaline-based染料敏化剂包含改进辅助受体和π-conjugation系统的刚度,从而导致优越的pc高达10.11％。Zhu的团队引入了一种基于喹喔啉敏化剂的固态DSSCs，其效率为11.7％，是固态DSSCs中效率最高的PCE。喹喔啉为基础的敏化剂在DSSCs中表现出巨大的潜力以获得优异的性能。然而，上述敏化剂大多含有喹喔啉单元上的两个分离的非共面基团。文献中很少提及由体积大、刚性和共面基喹啉衍生的敏化剂。据报道,引入刚性和共面单元的多环芳烃等有机染料大大优化DSSCs的性能主要是由于其相对较高的π-conjugation和移位。在这方面，我们重点研究一种新的结构调整策略，以提高基于喹喔啉敏化剂的光伏性能。在合成过程中，突出的创新是将主要的碳-碳联轴器简化为三组分一锅反应，具有很高的成本效益、时间和节能。通过将菲与杂环喹诺啉固化成二苯并[a,c]菲那嗪，提高敏化剂的刚性，进一步延长染料分子的有效共轭长度，拓宽吸收区域，减小光能隙。此外，在增感剂中加入两个烷基链，不仅可以防止染料的聚集，而且由于增感剂的尺寸较大，还可以抑制电子的重组，从而增加VOC。
发明内容
针对现有技术存在的上述问题，本申请人提供了一种以喹喔啉为辅助受体的具有高刚性结构的染料敏化剂及其作为光电转换材料在染料敏化太阳能电池器件上的应用。本发明化合物基于ICT光电转换机理，作为染料敏化剂应用于染料敏化太阳能电池，本发明制作的器件具有良好的光电性能，能够满足太阳能电池制造企业的要求。
本发明的技术方案如下：
一种以喹喔啉为辅助受体的具有高刚性结构的染料敏化剂，结构如通式(1)所示：
通式(1)中，R1表示为氢原子、正己基、十二烷基、叔丁基或苯基；
通式(1)中，R2表示为下列结构中的一种；
作为优选，所述的染料敏化剂为以下具体化合物中的一种：
本发明还提供了三组分一锅反应制备喹喔啉为辅助受体的具有高刚性结构的染料敏化剂的方法，包括：
根据文献合成了中间产物3b和10-己基-3-(4,4,5,5-四甲基-1,3,2-二恶硼烷-2-酰基)-10h-吩噻嗪。
关键前体醛6和6b合成好的收益率通过第一个碳碳偶联的13-dibromodibenzo[a、c]吩嗪(5)或10,13-dibromo-3,6-dihexyldibenzo[a、c]吩嗪(5b)和三苯胺在K2CO3溶液,Pb(PPh3)4和季铵氯化物336紧随其后的第二个碳碳耦合与5-formyl-2-thienylboronic酸罐完成后第一个碳碳耦合。以10-己基-3-(4,4,5,5-四甲基-1,3,2-二恶硼烷-2-酰基)-10h-吩噻嗪和5-甲酰基-2-噻吩硼酸为偶联剂，通过10,13-二溴-3,6-二己基二苯并[a,c]苯那嗪(5b)与10-己基-3,5-四甲基-1,3,2-二恶硼烷-2-酰基)的碳-碳偶联反应，在一锅中以类似于6a和6b的方法合成了醛6c。最后，以关键醛6a-6c为原料，分别与氰乙酸进行诺韦纳格尔缩合，合成了靶向敏化剂LY01-LY03。通过柱层析或重结晶纯化中间体和靶向染料敏化剂，得到目标产物；所有目标化合物均经FT-IR、1HNMR和HRMS表征。
反应式如下：
作为优选，所述喹喔啉化合物与给体和醛的摩尔比为1:1：1.2，与催化剂的摩尔比为1:0.05。
同现有技术相比，本发明有益的技术效果在于：
(1)在合成过程中，获得关键醛6a-6c的主要两种碳-碳耦合被简化为一锅三组分反应，具有较高的成本效益、时间和节能。与此同时本发明化合物都具有高的光电转化效率，丙二腈受体具有好的的化学稳定性和热稳定性，使得这类喹喔啉类染料分子作为光电转换材料具有较好的工业应用前景。
(2)本发明提供了一种显著提高电池光电压的分子工程调谐方法，通过长烷基链的掺入策略提高染料敏化剂的分子刚性，防止“权衡”效应，从而显著提高了无金属有机增敏剂的VOC。
附图说明
图1为本发明化合物应用的器件结构示意图；其中，1为透明导电基板层，2的TiO2阳极层，3染料层，4铂电极层。
图2为实施例3基于ly01-ly03的DSSCs的I-V特性。
图3为实施例3基于ly01-ly03的DSSCs的IPCE谱。
具体实施方式
下面结合附图和实施例，对本发明进行具体描述。
合成路线：
(1)化合物1的合成
在烧瓶中加入化合物5(3.25g,8.80mmol)、CSA(0.30g,1.28mmol)、乙二醇(10mL,179mmol)和干甲醇(50mL)。搅拌至120-130℃加热24h，冷却至RT后形成白色沉淀，真空过滤，用乙醇洗涤三次。产生化合物1(2.6克，60％)为淡黄色固体。1H NMR(500MHz,CDCl3)δ7.96(s,1H),7.63(s,1H),7.57(dd,J＝8.3,1.8Hz,1H),4.37–3.98(m,2H),3.88–3.43(m,2H).
(2)化合物2的合成
用烘干的250毫升三颈烧瓶装上化合物1(2.42g,5.20mmol)、Et2O(60mL)和THF(120mL)。混合物冷却到-78℃。然后用注射器滴入t-BuLi(1.66g,26.0mmol)。在-78℃下搅拌15min，加入白色正己基溴(4.26,26.0mmol)。快速形成白色沉淀物，除去冷却槽，在RT下搅拌过夜。溶剂在减压下被除去以产生有机残留物。将残渣溶解于CH2Cl2(100ml)中，用盐水(3×100ml)冲洗。有机部分在Na2SO4上干燥并过滤。减压脱溶剂，闪蒸柱层析(15:1己烷/乙酸乙酯)纯化残渣，得到化合物2(1.68g，收率69％)为白色蜡质固体。1H NMR(500MHz,CDCl3)δ7.71(s,1H),7.63(d,J＝7.9Hz,1H),7.22(d,J＝7.8Hz,1H),4.19(s,2H),3.67(s,2H),2.75–2.61(m,2H),1.76–1.59(m,2H),1.55(s,1H),1.48–1.22(m,5H),0.92(dt,J＝13.9,7.2Hz,3H).
(3)化合物3的合成
在250ml三颈烧瓶中，将化合物2(1.68g,2.15mmol)溶于CH2Cl2(40ml)、H2O(250ml)和乙腈(70ml)的混合溶剂中。然后加入TsOH·H2O(10.26g,54mmol)。将溶液加热至56℃回流过夜。冷却至RT后，将50ml饱和NaHCO3倒入溶液中。分离有机层，用CH2Cl2(3×100mL)萃取水层。合成的有机层在Na2SO4上干燥，然后过滤。在减压条件下除去溶剂，化合物3(0.75g,93％)为黄色蜡状固体。.1H NMR(500MHz,CDCl3)δ8.10(d,J＝7.9Hz,1H),7.79(s,1H),7.22(d,J＝7.8Hz,1H),2.75(td,J＝7.8,4.6Hz,2H),1.70(dd,J＝10.1,4.9Hz,2H),1.42(ddd,J＝25.9,13.1,5.4Hz,6H),0.98(t,J＝7.4Hz,3H).
(4)化合物4的合成
4,7-二溴-1,3-二氢苯并[c][1,2,5]噻二唑(2.7g,10mmol)在0℃干燥EtOH(100mL)中溶解。四批添加NaBH4(9.7g,256mmol)。10分钟后将混合物加热至室温，并持续搅拌一整夜。溶剂蒸发，残渣溶解于CH2Cl2(100mL)中，用盐水冲洗3次(3×100mL)，在无水Na2SO4上干燥。在较低的压力下，除去溶剂得到4(1.2g,45％)为白色固体。1H NMR(600MHz,CDCl3)δ6.84(s,1H).
(5)化合物5a的合成
在氩气气氛中，化合物4(0.73g,2.75mmol)和9,10-苯醌(0.57g,2.75mmol)溶于乙酸(80mL)中回流过夜。形成黄色沉淀，冷却至室温，过滤乙醇，再结晶得到化合物5a(1.10g,86％)为黄色固体。1H NMR(600MHz,CDCl3)δ9.56–9.34(m,1H),8.58(d,J＝8.0Hz,1H),8.03(s,1H),7.83(ddd,J＝36.1,11.6,4.2Hz,2H).
(6)化合物5b的合成
以化合物3b(0.75g,2.0mmol)和化合物4(0.53g,2.0mmol)为原料，合成了与化合物5a相似的化合物5b(1.20g,26.7％)。1H NMR(600MHz,CDCl3)δ9.22(d,J＝8.1Hz,1H),8.21(s,1H),7.89(s,1H),7.49(d,J＝8.1Hz,1H),2.91–2.74(m,2H),1.79–1.62(m,2H),1.46–1.22(m,6H),0.88(tt,J＝19.3,9.8Hz,3H).
(7)化合物6a的合成
将5ml 2m K2CO3水溶液、5ml乙醇和30ml甲苯混合，在氩气下加入化合物5a(0.219g,0.5mmol)和N,N-二苯基-4-(4,4,5,5-四甲基-1,3,2-二恶硼烷-2-酰基)苯胺(0.232g,0.5mmol)。在氩气下加入三滴相转移催化剂aliquat-336(甲基三辛基氯化铵)，使混合物反应40min，然后在混合物中溶解四价(三苯基膦)钯(0)(Pb(PPh3)4)(58mg,0.05mmol)。溶液在85℃下继续搅拌，直到反应完成。然后加入5-甲酰基-2-噻吩硼酸(94mg,0.6mmol)，在85℃回流过夜。反应结束后将混合物冷却至室温，然后用CH2Cl2萃取。用无水硫酸钠进一步干燥有机层，真空过滤。将所得溶剂除去，得到粗产物。然后用制备的薄层色谱法对粗品进行纯化，得到上述化合物6a(60mg,20％)为红色固体。1H NMR(600MHz,CDCl3)δ(ppm):10.02(s,1H),9.50–9.39(m,1H),9.34(t,J＝11.2Hz,1H),9.09(dd,J＝19.0,8.2Hz,1H),8.51(t,J＝9.3Hz,2H),8.28(t,J＝8.0Hz,1H),8.22(t,J＝10.5Hz,1H),7.96–7.59(m,11H),7.31–7.21(m,8H),7.02(dt,J＝25.6,13.4Hz,2H).
(8)化合物6b的合成
以N、N-二苯基-4-(4,4,5,5-四甲基-1,3,2-二恶硼烷-2-酰基)苯胺(74mg,0.2mmol)、5-甲酰基-2-噻吩硼酸(31mg,0.2mmol)和化合物5b(120mg,0.2mmol)为原料，按与化合物6a类似的工艺合成6b。然后用制备的薄层色谱对化合物进行纯化，得到化合物6b为红色固体(40mg,26％)1H NMR(600MHz,CDCl3)δ(ppm):10.01(s,1H),9.83(d,J＝18.7Hz,1H),9.37(d,J＝8.1Hz,1H),8.96(d,J＝8.1Hz,1H),8.26(dd,J＝16.6,7.9Hz,3H),7.89(dd,J＝15.9,5.8Hz,2H),7.83(t,J＝6.5Hz,3H),7.64(dd,J＝9.4,6.1Hz,2H),7.44(d,J＝8.1Hz,1H),7.35(t,J＝4.5Hz,1H),7.29–7.21(m,9H),7.03(t,J＝7.3Hz,2H),2.84(dd,J＝16.3,8.4Hz,4H),1.75(dd,J＝16.6,8.2Hz,4H),1.43–1.27(m,12H),0.84(dd,J＝12.2,6.9H z,6H).
(9)化合物6c的合成
以10-己基-3-(4,4,5,5-四甲基-1,3,2-二恶硼烷-2-酰基)-10h-吩噻嗪(69mg,0.17mmol)、化合物5b(102mg,0.17mmol)和5-甲酰基-2-噻吩硼酸(27mg,0.17mmol)为原料，按化合物6a的类似工艺合成6c。然后用制备的薄层色谱对化合物进行纯化，得到化合物6c为红色固体(42mg,29％)。1H NMR(500MHz,CDCl3)δ(ppm):10.05(s,1H),9.37(d,J＝8.2Hz,1H),8.99(d,J＝8.1Hz,1H),8.30(d,J＝3.9Hz,2H),8.23(d,J＝7.7Hz,1H),7.97–7.73(m,5H),7.66(d,J＝8.1Hz,1H),7.50(d,J＝8.1Hz,1H),7.21(t,J＝7.0Hz,2H),7.06(t,J＝6.7Hz,1H),6.96(dd,J＝13.0,7.7Hz,2H),3.98(t,J＝7.2Hz,2H),2.90(dd,J＝16.2,8.8Hz,4H),1.99–1.87(m,2H),1.82(dd,J＝12.8,9.3Hz,4H),1.56–1.33(m,18H),1.01–0.82(m,9H).
(10)染料敏化剂LY01的合成
在氩气气氛下，将化合物6a(30mg,0.05mmol)、氰乙酸(8mg,0.10mmol)、乙酸铵(14mg,0.19mmol)分别装入3颈烧瓶中，加入15mL冰醋酸。然后将混合物加热到120℃回流，直到反应完成。然后溶液在室温下冷却。在真空条件下形成深红色沉淀并过滤，残渣用乙酸洗涤三次，得到LY01(16mg,60％)为深红色固体。FT-IR(cm-1):3033(OH carboxylic),2223(CN),1696(C＝O),1585(C＝C aromatic),1488(C＝N aromatic amine).1H NMR(600MHz,CDCl3)δ(ppm):9.58(s,1H),8.89(s,1H),8.70(t,J＝22.8Hz,3H),8.47(s,1H),8.18(s,1H),8.00(d,J＝21.1Hz,2H),7.90–7.74(m,6H),7.66(d,J＝13.8Hz,1H),7.33(t,J＝7.9Hz,4H),7.21–6.92(m,8H).MS:m/z(C46H28N4O2S)found＝701.2002(calcd.701.2006for[M+H]+),error＝0.549ppm.
(11)染料敏化剂LY02的合成
以乙酸铵(15mg,0.14mmol)、氰乙酸(12mg,0.16mmol)、化合物6b(28mg,0.035mmol)为原料，采用与化合物LY01相似的工艺合成了深红色固体染料LY02(20mg,66％)。).FT-IR(cm-1):3061(OH carboxylic),2956,2929,2856(CH3),2223(CN),1682(C＝O),1590(C＝C aromatic),1427(C＝N aromatic amine).1H NMR(600MHz,DMSO)δ(ppm):9.12–8.95(m,1H),8.45(d,J＝3.3Hz,1H),8.43–8.32(m,1H),8.32–8.22(m,1H),8.20–8.01(m,2H),7.89(s,2H),7.64(dd,J＝25.6,8.0Hz,3H),7.47–7.37(m,5H),7.18(t,J＝14.0Hz,7H),7.11(dd,J＝25.6,8.5Hz,3H),2.73(dd,J＝18.7,8.9Hz,4H),1.71(d,J＝6.8Hz,4H),1.59–1.19(m,12H),1.02–0.82(m,6H).MS:m/z(C58H52N4O2S)found＝867.3749(calcd.867.3738for[M-H]+),error＝1.210ppm.
(12)染料敏化剂LY03的合成
以染料LY01为原料，乙酸铵(19mg,0.24mmol)、氰乙酸(15mg,0.6mmol)和化合物6c(50mg,0.06mmol)为原料合成了染料LY03(40mg,74％)黑色固体。FT-IR(cm-1):3066(OHcarboxylic),2955,2927,2856(CH3),2222(CN),1685(C＝O),1574(C＝C aromatic),1418(C＝N aromatic amine).1H NMR(500MHz,DMSO)δ(ppm):9.02–8.85(m,1H),8.37(d,J＝4.4Hz,1H),8.32(dd,J＝18.7,9.0Hz,1H),8.21–7.95(m,3H),7.79(s,2H),7.62–7.47(m,3H),7.42–6.87(m,8H),3.91(s,2H),2.68(s,4H),1.78(s,2H),1.65(s,4H),1.37(t,J＝37.9Hz,18H),0.97–0.75(m,9H).MS:m/z(C58H58N4O2S2)found＝905.3926(calcd.905.3928for[M-H]+),error＝0.220ppm.
本发明化合物可以作为光电转换材料材料使用，对本发明化合物LY01,LY02和LY03分别进行S1能级、T1能级、ΔE ST、振子强度f、HOMO/LUMO能级的测试与计算，结果如表1所示。
表1激发态氧化电位和最低电子跃迁(E0-0)
a,HOMO，最高占据分子轨道；ESOP＝E*，激发态氧化电位；ESOP＝EHOMO-E0-0；E0-0＝S0-S1，垂直激发能最低，单态-单态跃迁最低；GSOP＝EHOMO，基态氧化电位。E0-0是从DMF的吸收光谱开始计算的。b、GSOP在DMF中以0.1M[TBA][PF6]测定，扫描速率为50mV s-1。以Fc/Fc+为内标校正，加入0.63V.c换算为NHE,E*计算为GSOP-E0-0。对DMF中的一个复杂分子，在B3LYP/6-31G理论水平上计算d、理论EHOMO、ESOP和E0-0。
以下通过实施例3，说明本发明合成的化合物在器件中作为光电转化材料的应用效果。
实施例3
发光器件的如图1所示，具体包括：透明基板层1/ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TAPC，厚度70nm)/发光层5(PPT和化合物3按照30：70的重量比混掺，厚度30nm)/电子传输层6(PPT，厚度30nm)/电子注入层7(LiQ，厚度1nm)/阴极反射电极层8(Al，厚度10nm)。
具体制备过程如下：
采用文献报道的方法制备了厚度为10+5mm、纳米孔层厚度为10mm、散射层厚度为5mm(面积:0.18cm2)的双层TiO2光电极(10+5)。Fluorine-doped氧化锡(FTO)涂层的眼镜(2.2毫米厚度,表面电阻的8Ω/cm2,TEC 8,皮尔金顿)用洗涤剂洗净,水、丙酮和乙醇,顺序。然后将FTO玻璃板浸入40mM TiCl4水溶液中70℃浸泡30min，用水和乙醇冲洗。薄层(8-12μm厚)二氧化钛(Solaronix Ti-Nanoxide D/SP)被沉积在透明导电玻璃刮刀印刷干燥电极紧随其后在350℃连续10分钟和30分钟的500℃,散射层(5μm厚)二氧化钛粒子(Solaronix Ti-Nanoxide R/SP)印刷。二氧化钛电极加热气流在350℃下10分钟,其次是加热后30分钟。在500℃冷却到室温,二氧化钛电极治疗的40毫米水溶液在70℃ TiCl4 30分钟,然后用水洗和乙醇。电极在500℃下再次加热30分钟，冷却至80℃后浸入染料溶液中。以乙腈为原料，叔丁醇和DMSO为溶剂，以1:1:1的比例制备了0.3mM的染料溶液。将去氧胆酸作为共吸附剂加入染料溶液中，浓度为10mm，电极浸入染料溶液中，在25℃下保持20h，将染料吸附在TiO2表面。
制备对电极时，先用洗涤剂、水清洗预切FCO玻璃，EtOH中加入0.1M HCl，丙酮浴超声10min。这些洗TCO然后在350℃干了10分钟,不断在500℃ 30分钟。薄层Pt-paste(SolaronixPlatisol T/SP)在外交部印刷和印刷电极在500℃被治愈了10分钟,冷却设备制造前50℃。
光伏photon-to-current效率(IPCE)测量进行三明治细胞,是准备使用二氧化钛涂层工作电极和铂涂层电极,并密封使用40μm Syrlyn垫片通过加热的聚合物。氧化还原电解质(Solaronix,Iodolyte HI-30)由乙腈中0.6M DMPII、0.05M I2、0.1MLiI和0.5M TBP组成。
采用太阳能模拟器(WXS-155S-10)在上午1.5照度(光强:100mw cm-2)通过阳极一侧的导电玻璃照射密封电池，对电池进行光伏测量。入射光-电流转换效率(IPCE)的测量是在CEP-2000系统上进行的(邦高，Keiki有限公司)。器件的测试结果见表2以及图2和图3。
表2基于ly01-ly03的DSSCs的J-V特性
从以上数据应用来看，本发明化合物在染料敏化太阳能电池发光器件中具有良好的应用效果，具有良好的产业化前景。
虽然已通过实施例和优选实施方式公开了本发明，但应理解，本发明不限于所公开的实施方式。相反，本领域技术人员应明白，其意在涵盖各种变型和类似的安排。因此，所附权利要求的范围应与最宽的解释相一致以涵盖所有这样的变型和类似的安排。
Claims (6)
1.一种以喹喔啉为辅助受体的具有高刚性结构的染料敏化剂，结构如通式(1)所示：
通式(1)中，R1表示为氢原子、正己基、十二烷基、叔丁基或苯基；
通式(1)中，R2表示为下列结构中的一种；
2.根据权利要求1所述的染料敏化剂，为以下具体化合物中的一种：
3.一种如权利要求1或2所述的染料敏化剂的制备方法，其特征在于，包括以下步骤：
(1)化合物5a或5b与化合物(I)进行第一偶联反应，然后再与化合物(II)进行第二偶联反应，得到化合物6a或6b；
(2)化合物6a或化合物6b与氰乙酸进行诺韦纳格尔缩合，得到靶向敏化剂LY01-LY02；
反应式如下：
4.一种如权利要求1或2所述的染料敏化剂的制备方法，其特征在于，包括以下步骤：
(1)化合物5b与化合物(I)进行第一偶联反应，然后再与化合物(II)进行第二偶联反应，得到化合物6c；
(2)化合物6c与氰乙酸进行诺韦纳格尔缩合，得到靶向敏化剂LY03；
反应式如下：
。
5.一种如权利要求1或2所述的染料敏化剂的应用，其特征在于，所述的染料敏化剂用于太阳能电池制作领域。
6.根据权利要求5所述的染料敏化剂的应用，其特征在于，所述的染料敏化剂用作光电转化材料。
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