CN107011370B - 一种meso-位乙炔基桥联的D-π-A型BODIPY类染料及其制备方法 - Google Patents
一种meso-位乙炔基桥联的D-π-A型BODIPY类染料及其制备方法 Download PDFInfo
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/12—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being branched "branched" means that the substituent on the polymethine chain forms a new conjugated system, e.g. most trinuclear cyanine dyes
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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Abstract
本发明公开了一种meso‑位乙炔基桥联的D‑π‑A型BODIPY类染料及其制备方法。该类染料是通过先在芴、苯并二噻吩、吩噻嗪等基团上引入乙炔基,然后再与合成的meso‑位Cl取代的BODIPY单元通过Sonogashira偶联反应得到meso‑位乙炔基桥联的D‑π‑A型BODIPY类染料I。该类染料的合成方法简单,反应条件易于控制,产率较高,具有普遍适用性,可以高效合成;并可被广泛应用于能源、生命、分析、材料等科学领域,尤其适合作为有机小分子太阳能电池给体材料。
Description
技术领域:
本发明涉及一种meso-位乙炔基桥联的D-π-A型BODIPY类染料及其制备方法,该类染料可广泛应用于能源、环境、生命、分析、材料等科学领域,尤其适合作为有机小分子太阳能电池给体材料。
背景技术:
氟化硼络合二吡咯甲川(BODIPY)类化合物是近几十年才兴起并被广泛研究的一种新型荧光染料。它具有良好的稳定性、灵活的可修饰性、高的摩尔消光系数(1×105M-1cm-1)和较高的氧化电位。鉴于BODIPY类染料独特的光物理性质、化学性质以及可修饰性,可以通过在不同的活性位点引入不同的取代基或者改变共轭链长度等手段调节其光谱性质,增强其应用性。近几十年来,BODIPY类染料的飞速发展积累了深厚的研究基础,并被广泛应用于生物及化学分析检测、医药、太阳能电池等领域。尤其是长波长BODIPY类染料不但应用于荧光分析的前沿领域,而且在激光材料、化学传感器、小分子及聚合物太阳能电池等领域也有非常乐观的应用前景。
然而目前已开发的BODIPY类染料合成步骤冗长、种类有限、产率较低、分离提纯难度大,缺乏对分子光电性能的优化。因此使用较为简单的原料,通过简洁的合成路线,制备出不同优异性能的BODIPY类染料,都是亟需解决的难点。相关文献报道,在BODIPY母核的meso-位引入多种官能团后,由于空间位阻的影响,很难和氟硼核心平面形成有效的共轭,对染料分子的光谱性能影响很小,很难得到性能优异的meso-位取代的BODIPY染料,因而对于meso-位修饰的BODIPY类染料的研究报道比较少。本发明通过在给体单元与BODIPY单元的meso-位之间引入乙炔基作为桥联基团来改善分子的平面性以及拓宽分子的共轭长度,这更加有利于分子内的电荷传输和能量转移。
本发明通过Sonogashira偶联反应设计合成了一系列结构新颖的meso-位乙炔基桥联的D-π-A型BODIPY类染料,对该类染料的合成方法进行了优化,丰富了meso-位修饰的BODIPY类染料的种类,通过研究它们的光物理性质以及电化学行为,揭示了这类分子结构与性质之间的关系,这些目标分子的给体单元都具有良好的平面性以及较强的给电子能力,再加上以直线型乙炔基为桥联基团使得这些分子具有较宽较强的紫外吸收、较高的摩尔消光系数、比较稳定的光化学性质,为构建有机太阳能电池材料提供了新的思路。
发明内容:
本发明的目的在于从结构设计的角度出发,以直线型结构的乙炔基作为桥联基团,芴、苯并二噻吩和吩噻嗪等作为给体单元,设计合成出一种meso-位乙炔基桥联的D-π-A型BODIPY类染料,通过在给体单元与受体单元之间加入乙炔基作为桥联基团,使目标分子的平面性更好,有利于分子内的电荷传输,使其具有优良的光电性能,而且,目标分子具有新颖的分子结构、较宽的紫外吸收范围,可作为有机太阳能电池材料。
本发明的另一个目的是提供一种meso-位乙炔基桥联的D-π-A型BODIPY类染料的制备方法,其反应条件易于控制、产物纯化简单、产率较高、具有普适性。
为更好的实现上述目的,本发明采用以下技术方案:
一种meso-位乙炔基桥联的D-π-A型BODIPY类染料,具有通式I的化学结构:
式I中,D是给体单元,为以下几种结构单元中的一种:
n为1-20的自然数。
一种meso-位乙炔基桥联的D-π-A型BODIPY类染料的制备方法,包括以下步骤:
(1)在冰水浴条件下CSCl2与吡咯发生缩合反应得到中间体1,其结构为:
(2)中间体1在冰水浴条件下经双氧水氧化得到中间体2,其结构为:
(3)中间体2先与POCl3反应,然后再在碱性三乙胺作用下和三氟化硼乙醚发生螯合反应得到中间体3,其结构为:
(4)2-碘-9,9-二烷基芴与三甲基硅烷基乙炔进行Sonogashira偶联,再通过四丁基氟化铵脱去硅甲基,得到中间体4,其结构为:
(5)2-溴-4,8-二烷氧基苯并二噻吩与三甲基硅烷基乙炔进行Sonogashira偶联,再通过四丁基氟化铵脱去硅甲基,得到中间体5,其结构为:
(6)3-溴-N-烷基吩噻嗪与三甲基硅烷基乙炔进行Sonogashira偶联,再通过四丁基氟化铵脱去硅甲基,得到中间体6,其结构为:
(7)中间体3与中间体4经Sonogashira偶联反应,得到目标染料BDP1,其结构为:
(8)中间体3与中间体5经Sonogashira偶联反应,得到目标染料BDP2,其结构为:
(9)中间体3与中间体6经Sonogashira偶联反应,得到目标染料BDP3,其结构为:
作为上述技术方案的优选,步骤(1)~(9)反应中的反应介质为1,2-二氯乙烷、N,N-二甲基甲酰胺、甲醇、乙醇、四氢呋喃、二氯甲烷、三乙胺、甲苯、二甲基亚砜中的一种或几种混合。
作为上述技术方案的优选,步骤(4)~(9)中的Sonogashira偶联反应中所用催化剂为双三苯基膦二氯化钯和碘化亚铜中的一种或两种混合。
作为上述技术方案的优选,步骤(4)~(6)中的Sonogashira偶联反应中,反应底物与三甲基硅烷基乙炔的摩尔比为1:1~1:4。
作为上述技术方案的优选,步骤(4)~(6)中,Sonogashira偶联反应的反应温度为40~100℃。
作为上述技术方案的优选,步骤(7)~(9)中,所述反应的反应温度为0~50℃。
作为上述技术方案的优选,步骤(4)~(6)中,Sonogashira偶联反应的反应时间为12~36h。
作为上述技术方案的优选,步骤(7)~(9)中,所述反应的反应时间为10~60min。
本发明具有以下有益效果:
(1)本发明通过两步反应合成重要中间体3,最后再利用该中间体与多种带乙炔基的给体单元进行Sonogashira偶联反应,得到meso-位以乙炔基为桥联基团,分别以芴、苯并二噻吩和吩噻嗪为给体单元的一系列目标染料分子。
(2)本发明提供的制备方法反应条件易于控制,产物纯化简单,具有普适性。
(3)该类衍生物的光谱数据显示它们具有较稳定的光谱吸收、π-π堆积现象明显、Stokes位移明显;电化学结果显示其能级结构较低,与PC61BM能级匹配,在空气中稳定性较好;热失重分析显示,BDP1-3都具有良好的稳定性,说明它们在有机太阳能电池材料方面有潜在的应用价值。
附图说明:
图1:BDP 1的核磁氢谱图;
图2:BDP 1的核磁碳谱图;
图3:BDP 2的核磁氢谱图;
图4:BDP 2的核磁碳谱图;
图5:BDP 3的核磁氢谱图;
图6:BDP 3的核磁碳谱图;
图7:BDP 1的质谱图;
图8:BDP 2的质谱图;
图9:BDP 3的质谱图。
具体实施方式:
为了更好的理解本发明,下面通过实施例对本发明进一步说明,实施例只用于解释本发明,不会对本发明构成任何的限定。
1、中间体1的合成:
向装有恒压滴液漏斗的250mL三口瓶中加入CSCl2(10.00g,87mmol)和无水THF(30mL),将反应瓶置于0℃下搅拌20min,称取吡咯(11.67g,174mmol),溶解到无水THF(30mL)中并倒入恒压滴液漏斗,控制滴加速度加入到反应瓶中,0℃磁力搅拌1h。然后再加入无水MeOH(20mL),继续搅拌2h。停止反应,倒入100mL蒸馏水中,用乙酸乙酯萃取(50mL×3),有机相经饱和食盐水洗涤(50mL×3),无水Na2SO4干燥过夜。过滤收集滤液,减压蒸除溶剂,剩余物用硅胶(200-300目)柱层析[洗脱剂,V(石油醚):V(乙酸乙酯)=30:1]纯化得紫红色固状中间体1(3.52g),产率23%。1H NMR(400MHz,CDCl3)δ:9.78(s,2H),7.21(s,2H),7.08–7.01(m,2H),6.45–6.38(m,2H).13C NMR(101MHz,CDCl3)δ:193.08,138.38,127.79,114.92,112.56.
2、中间体2的合成:
向装有恒压滴液漏斗的250mL三口瓶中依次加入中间体1(2.00g,11.4mmol)、KOH(2.50g)和95%MeOH水溶液(30mL),将反应瓶置于0℃下磁力搅拌10min,量取30%的H2O2(25mL)倒入恒压滴液漏斗中,控制滴加速度加入到反应瓶中,继续搅拌10min。向反应瓶中加入100mL冰水,会析出大量白色固体,抽滤,滤饼真空干燥得白色固状中间体2(1.61g),产率91%。1H NMR(400MHz,CDCl3)δ:10.08(s,2H),7.17(s,2H),7.09(d,J=0.5Hz,2H),6.35(dt,J=4.7,2.5Hz,2H). 13C NMR(101MHz,CDCl3)δ:173.01,130.53,124.16,116.15,111.00.
3、中间体3的合成:
向250mL三口瓶中依次加入中间体2(1.60g,10mmol)和1,2-二氯乙烷(60mL),将体系抽真空,通入氩气保护,用注射器缓慢滴加POCl3(1.8mL),加热至85℃反应3h。冷却至室温后将反应装置移入冰水浴中,用注射器缓慢滴加Et3N(14mL),搅拌5min后,再用注射器控制滴加速度缓慢加入三氟化硼乙醚(14mL),转移至室温继续反应2h。停止反应,倒入100mL蒸馏水中,用二氯甲烷萃取(50mL×3),有机相经饱和食盐水洗涤(50mL×3),无水Na2SO4干燥过夜。过滤收集滤液,减压蒸除溶剂,剩余物用硅胶(200-300目)柱层析[洗脱剂,V(石油醚):V(乙酸乙酯)=20:1]纯化得红色固状中间体3(0.82g),产率36%。1H NMR(400MHz,CDCl3)δ:7.89(s,2H),7.41(d,J=4.2Hz,2H),6.58(d,J=4.3Hz,2H).13C NMR(101MHz,CDCl3)δ:145.06,141.17,134.02,129.34,119.15.MALDI-TOF-MS,m/z:calcd forC9H6BClF2N2[M-F-Cl]+:172.028,found:172.056.
4、中间体4的合成:
向100mL三口瓶中依次加入9,9-二甲基-2-碘芴(1.92g,6.0mmol)、CuI(0.12g,0.6mmol)、Pd(PPh3)2Cl2(0.29g,0.3mmol)和三乙胺(50mL),将体系抽真空,通入氩气保护,室温下缓慢滴加三甲基硅烷基乙炔(2.54mL,18mmol),然后将温度升至65℃反应24h。停止反应,冷却至室温,倒入100mL蒸馏水中,用二氯甲烷萃取(50mL×3),有机相经饱和食盐水洗涤(50mL×3),无水Na2SO4干燥过夜。过滤收集滤液,减压蒸除溶剂,剩余物用硅胶(200-300目)柱层析[洗脱剂,石油醚]纯化得白色固体(1.59g),产率91%。1H NMR(400MHz,CDCl3)δ:7.69–7.66(m,1H),7.62(d,J=7.8Hz,1H),7.54(s,1H),7.45(d,J=7.8Hz,1H),7.42–7.39(m,1H),7.33–7.28(m,2H),1.45(s,6H),0.28(s,9H).13C NMR(101MHz,CDCl3)δ:154.01,153.51,139.72,138.54,131.21,127.80,127.18,126.39,122.72,121.54,120.39,119.89,106.08,94.07,46.91,27.06,0.16.
其中,9,9-二甲基-2-碘芴可以被其他的9,9-二烷基-2-碘芴替换,烷基为碳原子数为1-20的烷基取代基。
向50mL单口瓶中,依次加入上一步合成的化合物(1.16g,4mmol)、THF(30mL)、四丁基氟化铵THF溶液(2mL),室温下磁力搅拌反应10min。停止反应,倒入50mL蒸馏水中,用乙酸乙酯萃取(50mL×3),有机相经饱和食盐水洗涤(50mL×3),无水Na2SO4干燥过夜。过滤收集滤液,减压蒸除溶剂,剩余物用硅胶(200-300目)柱层析[洗脱剂,石油醚]纯化得黄色油状中间体4(0.84g),产率96%。1H NMR(400MHz,CDCl3)δ:7.73–7.69(m,1H),7.67(d,J=7.8Hz,1H),7.56(s,1H),7.49(dd,J=7.8,1.4Hz,1H),7.44(dd,J=6.4,2.0Hz,1H),7.36–7.31(m,2H),3.13(s,1H),1.48(s,6H).13C NMR(101MHz,CDCl3)δ:153.94,153.55,139.97,138.39,131.26,127.86,127.17,126.52,122.72,120.41,119.94,84.50,46.89,27.02.MALDI-TOF-MS,m/z:calcd for C17H14[M]+:218.110;found 218.157.
5、中间体5的合成:
向装有恒压滴液漏斗的250ml三口瓶中依次加入4,8-二辛氧基苯并二噻吩(2.68g,6mmol)、二氯甲烷(30mL)、冰醋酸(30mL),称取N-溴代丁二酰亚胺(1.18g,6.6mmol)溶于二氯甲烷(30mL)并倒入恒压滴液漏斗,逐滴加入到反应瓶中,室温下磁力搅拌反应6h。停止反应,用饱和碳酸氢钠溶液调节至无气泡产生,用二氯甲烷萃取(50mL×3),有机相经饱和食盐水洗涤(50mL×3),无水Na2SO4干燥过夜。过滤收集滤液,减压蒸除溶剂,剩余物用硅胶(200-300目)柱层析[洗脱剂,石油醚]纯化得淡黄色液体(2.40g),产率76%。1H NMR(400MHz,CDCl3)δ:7.45(d,J=6.5Hz,2H),7.39(d,J=5.5Hz,1H),4.23(t,J=6.6Hz,4H),1.90–1.82(m,4H),1.55–1.27(m,20H),0.90(t,J=6.9Hz,6H).13C NMR(101MHz,CDCl3) δ:143.64,143.54,131.59,130.91,130.69,130.63,126.31,123.18,120.37,114.64,74.08,31.86,30.51,29.42,29.29,26.05,22.70,14.15.
其中,4,8-二辛氧基苯并二噻吩可以被其他4,8-二烷氧基苯并二噻吩取代,烷氧基为碳原子数为1-20的烷氧基取代基。
中间体5第二步的合成方法与中间体4第一步的合成方法类似,以上一步合成的淡黄色液体(2.1g,4mmol)为底物,纯化得黄色油状液体(1.85g),产率85%。1H NMR(400MHz,CDCl3)δ:7.60(s,1H),7.45(d,J=5.5Hz,1H),7.37(d,J=5.5Hz,1H),4.27–4.21(m,4H),1.86(dd,J=7.2,4.7Hz,4H),1.32(m,20H),0.90(t,J=6.8Hz,6H),0.28(s,9H).13C NMR(101MHz,CDCl3)δ:144.64,143.85,132.77,130.67,130.45,129.98,126.84,126.34,122.42,120.37,101.25,97.98,74.18,31.84,30.53,29.41,29.28,26.05,22.68,14.13,0.19.
中间体5第三步的合成方法与中间体4第二步的合成方法类似,以上一步合成的黄色油状液体(1.63g,3mmol)为底物,纯化得黄色油状液体中间体5(1.34g),产率95%。1HNMR(400MHz,CDCl3)δ:7.65(s,1H),7.45(d,J=2.1Hz,1H),7.36(d,J=5.6Hz,1H),4.27–4.23(m,4H),3.45(s,1H),1.84(dd,J=10.5,4.4Hz,4H),1.38–1.27(m,20H),0.90(t,J=6.4Hz,6H).13C NMR(101MHz,CDCl3)δ:144.70,143.91,132.89,131.63,130.49,129.94,126.74,125.99,121.22,120.36,83.04,77.50,74.18,31.87,30.54,29.44,29.31,26.09,22.70,14.15.MALDI-TOF-MS,m/z:calcd for C28H38O2S2[M]+:470.231;found 470.227.
6、中间体6的合成
向250mL三口瓶中依次加入N-辛基吩噻嗪(3.11g,10mmol)和无水DMF(100mL),装上恒压滴液漏斗,称取N-溴代丁二酰亚胺(1.96g,11mmol)溶于干燥的DMF(30mL)并加入到恒压滴液漏斗,逐滴加入到反应瓶中,室温下磁力搅拌反应12h。停止反应,用二氯甲烷萃取,饱和食盐水洗涤,用无水硫酸镁干燥。过滤,滤液旋转蒸发去除溶剂,粗产品用硅胶(200-300目)柱层析[洗脱液,石油醚]纯化得黄色油状液体中间体6(3.55g),产率91%。1HNMR(400MHz,CDCl3)δ:7.22(dd,J=5.5,1.9Hz,2H),7.17–7.09(m,2H),6.92(dd,J=7.5,1.0Hz,1H),6.84(d,J=8.2Hz,1H),6.69–6.67(m,1H),3.83–3.76(m,2H),1.75(dd,J=14.7,7.4Hz,2H),1.26(dd,J=10.7,7.1Hz,10H),0.87(d,J=6.7Hz,3H).13C NMR(101MHz,CDCl3)δ:144.53,130.13,129.83,129.73,129.63,127.45,127.23,124.19,122.65,116.52,115.53,114.39,47.52,31.75,29.19,26.90,26.78,26.65,22.64,14.11.
其中,N-辛基吩噻嗪可以被其他N-烷基吩噻嗪取代,烷基为碳原子数为1-20的烷基取代基。
中间体6第二步的合成方法与中间体4第一步的合成方法类似,以上一步合成的黄色油状液体(1.95g,5mmol)为底物,纯化得黄色油状液体(1.59g),产率78%。 1H NMR(400MHz,CDCl3)δ:7.23–7.18(m,3H),7.10(ddd,J=10.8,9.0,4.4Hz,2H),6.89(t,J=7.0Hz,1H),6.71(dd,J=8.4,2.8Hz,1H),3.82–3.77(m,2H),1.77–1.72(m,2H),1.29–1.23(m,10H),0.87(t,J=6.6Hz,3H),0.23(s,9H).13C NMR(101MHz,CDCl3)δ:144.64,130.65,130.58,129.97,129.64,127.45,127.30,124.21,122.69,116.64,115.49,114.85,104.61,93.70,47.55,31.76,29.20,26.87,26.78,26.64,22.64,14.12,0.07.
中间体6第三步的合成方法与中间体4第二步的合成方法类似,以上一步合成的黄色油状液体(1.22g,3mmol)为底物,纯化得黄色油状中间体6(0.94g),产率93%。1H NMR(400MHz,CDCl3)δ:7.25–7.19(m,3H),7.17–7.05(m,2H),6.90(td,J=7.5,0.9Hz,1H),6.75–6.72(m,1H),3.83–3.77(m,2H), 3.02(s,1H),1.79–1.73(m,2H),1.26(m,10H),0.87(t,J=6.6Hz,3H). 13C NMR(101MHz,CDCl3)δ:144.60,131.31,130.72,130.03,129.69,127.48,127.37,124.15,122.77,116.69,115.55,114.94,83.16,76.85,47.56,31.76,29.22,29.20,26.90,26.80,22.65,14.13.MALDI-TOF-MS,m/z:calcd for C22H25NS[M]+:335.171;found 335.184.
实施例1
BDP1的合成:
向50mL三口瓶中依次加入中间体3(226mg,1.0mmol)、中间体4(262mg,1.2mmol)、无水THF(20mL)和无水Et3N(2mL),将体系抽真空,通入氩气保护,将反应瓶置于冰水浴中,氩气氛围下迅速加入CuI(10mg,0.05mmol)和Pd(PPh3)2Cl2(35mg,0.05mmol),0℃磁力搅拌30min。停止反应,倒入50mL蒸馏水中,用乙酸乙酯萃取(30mL×3),有机相经饱和食盐水洗涤(30mL×3),无水Na2SO4干燥过夜。过滤收集滤液,减压蒸除溶剂,剩余物用硅胶(200-300目)柱层析[洗脱剂,V(石油醚):V(乙酸乙酯)=16:1]纯化得红色固体BDP1(290mg),产率71%。1H NMR(400MHz,CDCl3)δ:7.84(s,2H),7.82–7.77(m,2H),7.70(d,J=0.7Hz,1H),7.67(dd,J=7.8,1.4Hz,1H),7.51–7.45(m,3H),7.44–7.37(m,2H),6.58(d,J=3.4Hz,2H),1.55(s,6H).13C NMR(101MHz,CDCl3)δ:154.32,154.06,143.31,142.55,137.85,136.51,132.42,128.96,128.79,127.74,127.44,127.08,122.88,120.93,120.46,119.07,118.26,107.72,84.82,47.09,26.99.MALDI-TOF-MS,m/z:calcd for C26H19BF2N2[M-F]+:389.163,found:389.206.
实施例2
BDP2的合成:
BDP2的合成方法与BDP1的合成方法类似,以中间体3(226mg,1.0mmol)和中间体5(564mg,1.2mmol)作为底物,纯化得深红色固体BDP2(390mg),产率59%。 1H NMR(400MHz,CDCl3)δ:7.94(s,1H),7.85(s,2H),7.49(q,J=5.6Hz,2H),7.43(d,J=4.0Hz,2H),6.59(d,J=3.3Hz,2H),4.35(t,J=6.6Hz,2H),4.28(t,J=6.6Hz,2H),1.96–1.86(m,4H),1.35(d,J=25.9Hz,20H),0.90(dd,J=6.7,4.7Hz,6H).13C NMR(101MHz,CDCl3)δ:145.67,143.90,143.68,136.16,134.22,131.02,130.62,130.46,130.40,128.98,128.15,126.37,120.44,119.62,118.51,99.68,90.05,74.42,74.18,31.88,30.56,29.45,29.34,26.08,22.73,14.19.MALDI-TOF-MS,m/z:calcd for C37H43BF2N2O2S2[M]+:660.283,found:660.183.
实施例3
BDP3的合成:
BDP3的合成方法与BDP1的合成方法类似,以中间体3(226mg,1.0mmol)和中间体6(402mg,1.2mmol)作为底物,纯化得紫黑色固体BDP3(326mg),产率62%。 1H NMR(400MHz,CDCl3)δ:7.81(s,2H),7.45(dd,J=8.5,1.9Hz,1H),7.39–7.34(m,3H),7.18(dd,J=11.1,4.5Hz,1H),7.12(dd,J=7.6,1.5Hz,1H),6.97(t,J=7.0Hz,1H),6.87(dd,J=14.6,8.2Hz,2H),6.55(d,J=2.8Hz,2H),3.92–3.85(m,2H),1.81(dd,J=14.9,7.6Hz,2H),1.56–1.18(m,10H),0.87(t,J=6.8Hz,3H).13C NMR(101MHz,CDCl3)δ:148.06,143.63,142.77,136.21,132.82,131.28,128.51,127.76,127.65,127.57,125.05,123.49,118.04,115.93,115.12,114.05,107.56,107.52,85.76,47.88,31.76,29.23,29.19,26.85,26.76,22.66,14.15.MALDI-TOF-MS,m/z:calcd for C31H30BF2N3S[M]+:525.222,found:525.203.
上述实施例中目标染料BDP1-3的光物理及热稳定性相关数据见表1,电化学性质的相关数据见表2。
表1 BDP 1-3的光物理及热稳定性相关数据
a measured in CH2Cl2solution.b measured in the neat film.
表1结果显示,在二氯甲烷中,目标染料BDP1-3的最大吸收波长分别为537、549和538nm,与中间体3(503nm)相比,BDP1-3的紫外吸收光谱出现了34-46nm的红移,这说明在meso-位引入的带乙炔基的给电子单元与BODIPY单元之间形成了有效的共轭,体系的共轭长度增加,使得分子的光学带隙减少。BDP1-3的红移排序为BDP2>BDP3>BDP1。BDP2的红移程度最大可能是因为苯并二噻吩具有较强的给电子能力,同时BDP2的平面性较好。从表1可以得到目标染料BDP1-3的摩尔消光系数分别为0.42×105,0.37×105和0.51×105。说明在BODIPY的meso-位引入带乙炔基的给体单元可以拓宽BODIPY染料的光谱吸收范围,有利于提高染料对光的吸收。
在固体膜中BDP1-3的最大吸收波长依次为560、573和562nm,与溶液中的吸收光谱相比依次红移了23、24和24nm,可以看出它们都产生了较大的红移,而且吸收光谱的范围变得更为宽阔。这主要是因为固态下分子的π-π堆积导致分子之间形成了额外的π共轭,有效的延长了共轭长度,从而使它们的最大吸收光谱红移和拓宽。固态下优异的光谱吸收性能将为该类染料在有机小分子太阳能电池方面的研究奠定基础。
分别以BDP1-3的最大吸收波长为激发波长进行激发,这三种染料分子在500-700nm之间均表现出单一的发射光谱带,发射波长分别为561、554、544nm,这说明BDP1-3在溶液中产生了明显的Stokes位移(5-24nm)。我们可以推断出BDP1-3的荧光发射属性为ICT发射。BDP2和BDP3产生的Stokes位移相对较小,而BDP1具有较大的Stokes位移,可能是由于BDP1的平面性更好,更有利于芴与BODIPY单元的激发态分子内能量传递。
根据热失重分析测试显示,BDP1-3在失重5%时的热分解温度分别为278、303和285℃。显然,BDP1-3具有良好的的热稳定性,而良好的热稳定性有利于它们在小分子太阳能电池领域的应用。
表2 BDP 1-3的循环伏安数据
a Eg was estimated from the absorption thresholds from absorptionspectra of dyes absorbed in solution,Eg=1240/λonset.
b Eox onset,onset oxidation potential
c E red the reduction potential,was calculated from Eox onset–Eg.
dEHOMO=[-(Eox onset-0.52)-4.8]eV,ELUMO=EHOMO+Eg eV.
从表2可以看出,BDP1-3的起始氧化电位分别是1.38、1.04和0.87eV,根据公式计算得相应的HOMO能级分别为:-5.66、-5.34和-5.15eV;LUMO能级分别为:-3.53、-3.55和-3.41eV。这说明,当以乙炔基为桥联基团时,meso-位所含的不同取代基团对分子的氧化电位有明显的影响。我们可以通过在meso-位以平面性好的基团为桥联基团,然后再引入合适的官能团进行修饰实现对分子能级的有效调控,从而得到性能优异的BODIPY染料。三种染料的能带隙分别为2.13、1.79和1.74eV。同时还可以看出它们的能级均处在比较低的水平,适合应用于小分子太阳能电池领域。
本发明通过上述实施例来说明本发明的详细合成方法,但本发明并不局限于上述方法,即不意味着本发明必须依赖上述反应条件才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明反应溶剂催化剂的等效替换及反应具体条件的改变等,均落在本发明的保护范围和公开范围之内。
Claims (9)
1.一种meso-位乙炔基桥联的D-π-A型BODIPY类染料,其特征在于,具有通式I的化学结构:
式I中,D是给体单元,为以下几种结构单元中的一种:
n为1-20的自然数。
2.如权利要求1所述的一种meso-位乙炔基桥联的D-π-A型BODIPY类染料的制备方法,其特征在于,包括以下步骤:
(1)在冰水浴条件下CSCl2与吡咯发生缩合反应得到中间体1,其结构为:
(2)中间体1在冰水浴条件下经双氧水氧化得到中间体2,其结构为:
(3)中间体2先与POCl3反应,然后再在碱性三乙胺作用下和三氟化硼乙醚发生螯合反应得到中间体3,其结构为:
(4)2-碘-9,9-二烷基芴与三甲基硅烷基乙炔进行Sonogashira偶联,再通过四丁基氟化铵脱去硅甲基,得到中间体4,其结构为:
(5)2-溴-4,8-二烷氧基苯并二噻吩与三甲基硅烷基乙炔进行Sonogashira偶联,再通过四丁基氟化铵脱去硅甲基,得到中间体5,其结构为:
(6)3-溴-N-烷基吩噻嗪与三甲基硅烷基乙炔进行Sonogashira偶联,再通过四丁基氟化铵脱去硅甲基,得到中间体6,其结构为:
(7)中间体3与中间体4经Sonogashira偶联反应,得到目标染料BDP1,其结构为:
(8)中间体3与中间体5经Sonogashira偶联反应,得到目标染料BDP2,其结构为:
(9)中间体3与中间体6经Sonogashira偶联反应,得到目标染料BDP3,其结构为:
3.如权利要求2所述的一种meso-位乙炔基桥联的D-π-A型BODIPY类染料的制备方法,其特征在于,步骤(1)~(9)反应中的反应介质为1,2-二氯乙烷、N,N-二甲基甲酰胺、甲醇、乙醇、四氢呋喃、二氯甲烷、三乙胺、甲苯、二甲基亚砜中的一种或几种混合。
4.如权利要求2所述的一种meso-位乙炔基桥联的D-π-A型BODIPY类染料的制备方法,其特征在于,步骤(4)~(9)中的Sonogashira偶联反应中所用催化剂为双三苯基膦二氯化钯和碘化亚铜中的一种或两种混合。
5.如权利要求2所述的一种meso-位乙炔基桥联的D-π-A型BODIPY类染料的制备方法,其特征在于,步骤(4)~(6)中的Sonogashira偶联反应中,反应底物与三甲基硅烷基乙炔的摩尔比为1:1~1:4。
6.如权利要求2所述的一种meso-位乙炔基桥联的D-π-A型BODIPY类染料的制备方法,其特征在于,步骤(4)~(6)中,Sonogashira偶联反应的反应温度为40~100℃。
7.如权利要求2所述的一种meso-位乙炔基桥联的D-π-A型BODIPY类染料的制备方法,其特征在于,步骤(7)~(9)中,所述反应的反应温度为0~50℃。
8.如权利要求2所述的一种meso-位乙炔基桥联的D-π-A型BODIPY类染料的制备方法,其特征在于,步骤(4)~(6)中,Sonogashira偶联反应的反应时间为12~36h。
9.如权利要求2所述的一种meso-位乙炔基桥联的D-π-A型BODIPY类染料的制备方法,其特征在于,步骤(7)~(9)中,所述反应的反应时间为10~60min。
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