CN108586315B - 一种苯并咔唑类化合物及其制备方法与应用 - Google Patents
一种苯并咔唑类化合物及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种苯并咔唑类化合物及其制备方法与应用,其应该具体是将该类化合物作为太阳能染料敏化剂的应用。所述苯并咔唑类化合物的合成方法为:将式IV化合物与氰基乙酸与有机溶剂混合,在哌啶的作用下,在氮气保护下,加热回流搅拌反应8~12h,反应完全后,旋干溶剂,残余物用洗脱剂溶剂进行硅胶柱层析,获得式I、式II或式III所示的苯并咔唑类太阳能染料敏化剂。本发明所述的苯并咔唑化合物可以作为染料敏化剂应用于染料敏化太阳能电池,为染料敏化剂的筛选增添了新的可应用物质。
Description
技术领域
本发明涉及一种苯并咔唑类化合物及其制备方法与应用,具体为作为染料敏化剂在染料敏化太阳能电池中的应用。
背景技术
染料敏化太阳能电池将具有分子内电荷迁移系(ICT)的大π共轭结构有机染料键合到半导体表面上,借助于染料对可见光的强吸收将半导体光谱响应拓宽到可见光区甚至红外区,产生光电流,模仿自然界绿色植物光合作用把光能转化为电能。与第一代晶体硅太阳能电池和第二代多元化合物薄膜太阳能电池相比,作为第三代太阳能电池的染料敏化太阳能电池(DSSCs),具有成本低、工艺简单、可弱光发电和光电转换效率高等优点。
在染料敏化太阳能电池(DSSCs)中,非金属有机染料敏化剂由于其结构灵活可修饰、摩尔吸光系数高、成本低、环境友好等优势引起越来越多的关注。近些年来,咔唑衍生物由于其独特的电子、光学性质和显著的热稳定性,已广泛应用在有机发光二极管(OLED)和有机光伏电池(OPⅤ)中。苯并[a]咔唑作为一个π扩展咔唑衍生物,具有较强的电子离域和分子内电荷转移的潜力,其在光电材料领域开始逐渐发挥其重要作用。本发明以苯并咔唑为电子给体,苯、呋喃和噻吩为π桥,以氰基乙酸为电子受体,设计并合成了三个D-π-A型苯并咔唑类染料敏化剂I~Ⅲ。
发明内容
本发明的目的是提供一种具有新颖结构的苯并咔唑类化合物及其制备方法与应用,本发明主要将该苯并咔唑类化合物作为太阳能染料敏化剂用于染料敏化太阳能电池中。
所述的一种苯并咔唑类化合物,其特征在于其结构如式(I)、式(Ⅱ)或式(Ⅲ)所示:
所述的苯并咔唑类化合物的制备方法,其特征在于所述制备方法如下:
在极性有机溶剂中,哌啶存在下,将氰基乙酸分别与式(Ⅳa)、式(Ⅳb)、式(Ⅳc)所示的化合物进行缩合反应,反应完全后,所得反应混合液经后处理分别得到式(I)、式(Ⅱ)或式(Ⅲ)所示的化合物;
所述的苯并咔唑类化合物的制备方法,其特征在于氰基乙酸与式(Ⅳa)、式(Ⅳb)、式(Ⅳc)所示的化合物的投料摩尔比为2~4:1。
所述的苯并咔唑类化合物的制备方法,其特征在于哌啶与式(Ⅳa)、式(Ⅳb)、式(Ⅳc)所示的化合物的摩尔比为3~10:1。
所述的苯并咔唑类化合物的制备方法,其特征在于有机溶剂为氯仿、乙腈或四氢呋喃中的一种或多种。
所述的苯并咔唑类化合物的制备方法,其特征在于有机溶剂的体积用量以式(Ⅳa)、式(Ⅳb)、式(Ⅳc)所示的化合物的物质的量计为5~12mL/mmol。
所述的苯并咔唑类化合物的制备方法,其特征在于缩合反应的温度为60~80℃,反应时间为8~12h。
所述的苯并咔唑类化合物的制备方法,其特征在于反应混合液的后处理方法为:反应结束后,所得反应混合液蒸除溶剂后,残余物用洗脱溶剂进行硅胶柱层析,以二氯甲烷、甲醇及醋酸的混合溶液为洗脱剂,收集含目标化合物的洗脱液,浓缩干燥分别得式(I)、式(Ⅱ)或式(Ⅲ)所示的苯并咔唑类化合物。
所述的苯并咔唑类化合物的制备方法,其特征在于洗脱溶剂为体积比为400:4:1的二氯甲烷、甲醇和醋酸的混合溶剂。
本发明对所述式(Ⅳa)、式(Ⅳb)、式(Ⅳc)所示化合物的来源没有特殊要求,采用市售或本领域技术人员公知的制备方法制备均可;
在本发明实施例中,所述式(Ⅳa)、式(Ⅳb)、式(Ⅳc)所示化合物优选采用如下方法制备得到,包括以下步骤:
在N2保护的条件下,将式(Ⅴ)所示的化合物、四三苯基膦钯与式(Ⅵa)、式(Ⅵb)、式(Ⅵc)甲酰基芳基硼酸化合物溶于四氢呋喃中,得到四氢呋喃溶液,将所述四氢呋喃溶液与碳酸钾水溶液混合进行加热回流,得到具有式(Ⅳa)、式(Ⅳb)、式(Ⅳc)所示结构的化合物;
本发明还公开了所述的苯并咔唑类化合物作为染料敏化剂在染料敏化太阳能电池中的应用,其制备方法简单、后处理方便,得到的产物具体的应用如下:
将本发明的苯并咔唑类化合物溶于氯仿-甲醇(Ⅴ:Ⅴ=10:1)的混合溶剂中,浸泡二氧化钛纳米粒子膜光电极24小时,得到负载了所述的苯并咔唑类化合物的二氧化钛电极,再将其与铂对电极组装成三明治结构的电池,并在电池边缘滴入电解质,利用毛细渗透原理将电解质引入电池内部,与100mⅤ/cm2光强照射下,测定光电压-电流特性曲线,其结果表明,以此类苯并咔唑类化合物作为太阳能染料敏化剂制作的染料敏化太阳能电池的光电转化效率在5.10-7.67%之间。
附图说明
图1为基于式(I)、式(Ⅱ)或式(Ⅲ)所示的化合物作为染料敏化剂的太阳能电池的光电流-电压曲线图。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
实施例1:式(I)所示的苯并咔唑类化合物的制备
1)式(Ⅳa)化合物的制备:取式(Ⅴ)所示的化合物(0.71g,2mmol)、式(Ⅵa)所示的4-甲酰基苯硼酸(0.36g,2.4mmol)和Pd(PPh3)4(0.23g,0.2mmol)溶于四氢呋喃(10mL)中,滴加2mol/L的K2CO3溶液(4mL),N2保护下加热回流10h,反应结束后用水(100mL)和二氯甲烷(100mL)萃取,有机层旋干溶剂,PE:EA=10:1硅胶柱层析分离提纯,得到黄色油状液体即为式(Ⅳa)所示的化合物(0.53g),收率70%。1H NMR(500MHz,CDCl3)δ:10.16(s,1H),8.63(d,J=8.5Hz,1H),8.17-8.16(m,2H),8.07-8.05(m,3H),7.79(d,J=8.0Hz,2H),7.68(t,J=7.2Hz,1H),7.62(d,J=8.3Hz,1H),7.56-7.49(m,2H),7.35(t,J=7.4Hz,1H),4.86(t,J=7.5Hz,2H),2.16-2.09(m,2H),1.65-1.57(m,2H),1.08(t,J=7.4Hz,3H);HREIMS m/z378.1852[M+H]+,cacld C27H24NO for:378.1858。
2)式(I)所示的苯并咔唑类化合物的制备:取步骤1)得到的式(Ⅳa)所示的化合物(0.19g,0.5mmol)和氰基乙酸(0.09g,1.05mmol)溶于氯仿(6mL)中,加入哌啶(0.5mL),N2保护下加热回流10h,反应结束后用二氯甲烷(100mL)和稀盐酸(100mL)萃取,有机层旋干溶剂,HAc:MeOH:CH2Cl2=1:4:400硅胶柱层析分离提纯,得到褐色固体式(I)所示的苯并咔唑类化合物(0.12g,54%)。m.p.224~226℃;1H NMR(500MHz,DMSO)δ:8.71(d,J=8.7Hz,1H),8.30-8.27(m,2H),8.10-8.07(m,3H),8.01(d,J=8.5Hz,1H),7.84(d,J=8.4Hz,1H),7.75-7.70(m,3H),7.57(t,J=7.5Hz,1H),7.51(t,J=7.6Hz,1H),7.29(t,J=7.4Hz,1H),4.93(t,J=7.2Hz,2H),1.97-1.91(m,2H),1.49-1.42(m,2H),0.95(t,J=7.4Hz,3H);HREIMS m/z 445.1916[M+H]+,cacld C30H25N2O2for:445.1916。
其反应方程式如下:
实施例2式(Ⅱ)所示的化合物的制备
1)式(Ⅳb)所示的化合物的制备:取式(V)所示的化合物(0.71g,2mmol),式(Ⅵb)所示的5-甲醛基呋喃-2-硼酸(0.34g,2.4mmol)和Pd(PPh3)4(0.23g,0.2mmol)溶于四氢呋喃(10mL)中,滴加2mol/L的K2CO3溶液(4mL),N2保护下加热回流10h。反应结束后用水(100mL)和二氯甲烷(100mL)萃取,有机层旋干溶剂,PE:EA=10:1硅胶柱层析分离提纯,得到橙黄色液体式(Ⅳb)所示的化合物(0.50g,67.7%)。1H NMR(500MHz,CDCl3)δ:9.76(s,1H),8.58-8.55(m,3H),8.20(d,J=7.8Hz,1H),7.70-7.67(m,1H),7.63(t,J=8.0Hz,1H),7.58(d,J=8.2Hz,1H),7.54(t,J=7.5Hz,1H),7.49(d,J=3.7Hz,1H),7.37(t,J=7.0Hz,1H),6.94(d,J=3.6Hz,1H),4.78(t,J=8.0Hz,2H),2.11-2.05(m,2H),1.62-1.55(m,2H),1.06(t,J=7.4Hz,3H).
2)式(Ⅱ)所示的化合物的制备:取式(Ⅳb)所示的化合物(0.73g,2mmol)和氰基乙酸(0.51g,6.0mmol)溶于四氢呋喃(10mL)中,加入哌啶(1.4mL),N2保护下加热回流10h。反应结束后用二氯甲烷(100mL)和稀盐酸(100mL)萃取,有机层旋干溶剂,HAc:MeOH:CH2Cl2=1:4:400硅胶柱层析分离提纯,得到橙色固体式(Ⅱ)所示的化合物(0.34g,38.6%)。m.p.215~217℃;1H NMR(500MHz,DMSO)δ:8.82(s,1H),8.73-8.69(m,2H),8.27(d,J=7.8Hz,1H),7.88-7.86(m,2H),7.79(t,J=7.5Hz,1H),7.70(t,J=7.5Hz,1H),7.54(t,J=7.3Hz,1H),7.40(d,J=3.5Hz,1H),7.34(t,J=7.4Hz,1H),7.28-7.24(m,1H),4.93(t,J=7.5Hz,2H),1.97-1.88(m,2H),1.48-1.39(m,2H),0.94(t,J=7.5Hz,3H);HREIMS m/z435.1702[M+H]+,cacld C28H23N2O3for:435.1709。
其反应方程式如下:
实施例3式(Ⅲ)所示的苯并咔唑类化合物的制备
1)式(Ⅳc)所示化合物的制备:取式(V)所示的(1.06g,3mmol),式(Ⅵc)所示的5-甲醛基噻吩-2-硼酸(0.56g,3.6mmol)和Pd(PPh3)4(0.35g,0.3mmol)溶于四氢呋喃(15mL)中,滴加2mol/L的K2CO3溶液(6mL),N2保护下加热回流10h。反应结束后用水(100mL)和二氯甲烷(100mL)萃取,有机层旋干溶剂,PE:EA=10:1硅胶柱层析分离提纯,得到黄绿色液体式(Ⅳc)所示化合物(0.76g,66.3%)。1H NMR(500MHz,CDCl3)δ:10.00(s,1H),8.59(d,J=8.5Hz,1H),8.54-8.48(m,1H),8.38(d,J=8.1Hz,1H),8.32(s,1H),8.16(d,J=7.8Hz,1H),7.89(d,J=3.7Hz,1H),7.69(t,J=8.0Hz,1H),7.59(t,J=8.0Hz,2H),7.56(d,J=4.0Hz,1H),7.37(d,J=7.1Hz,1H),4.80(t,J=7.5Hz,2H),2.12-2.06(m,2H),1.63-1.55(m,2H),1.07(t,J=7.5Hz,3H).
2)式(Ⅲ)所示的苯并咔唑类化合物的制备:取式(Ⅳc)所示化合物(1.15g,3mmol)和氰基乙酸(1.03g,12mmol)溶于乙腈(27mL)中,加入哌啶(1mL),N2保护下加热回流10h。反应结束后用二氯甲烷(100mL)和稀盐酸(100mL)萃取,有机层旋干溶剂,HAc:MeOH:CH2Cl2=1:4:400硅胶柱层析分离提纯,得到橙色固体式(Ⅲ)所示的苯并咔唑类化合物(0.40g,29.3%)。m.p.220~221℃;1H NMR(500MHz,DMSO)δ:13.79(bs,1H),8.74(d,J=8.6Hz,1H),8.62(s,1H),8.54(s,1H),8.36(d,J=7.8Hz,1H),8.31(d,J=8.4Hz,1H),8.17(d,J=4.0Hz,1H),7.87(d,J=8.5Hz,1H),7.80(t,J=7.3Hz,1H),7.68(t,J=8.0Hz,1H),7.60(d,J=3.6Hz,1H),7.54(t,J=7.4Hz,1H),7.36-7.30(m,1H),4.95(t,J=7.3Hz,2H),1.98-1.88(m,2H),1.49-1.41(m,2H),0.94(t,J=7.4Hz,3H);HREIMS m/z 451.1476[M+H]+,cacld C28H23N2O2S for:451.1480。
其反应方程式如下:
实施例4:
苯并咔唑类化合物作为染料敏化剂的应用
利用丝网印刷制备的双层TiO2纳米粒子膜作为光电极:首先在导电玻璃FTO上印一层12μm厚的20nm的TiO2粒子,于450℃下马弗炉内煅烧30min。在浸染料之前将烧好的膜浸入0.04mol·L-1的TiCl4水溶液70℃预处理30min,然后分别用水和乙醇冲洗,电吹风吹干。经马弗炉450℃下再次煅烧30min后,冷却至80℃后浸入3×10-4mol·L-1染料的氯仿-甲醇(Ⅴ:Ⅴ=10:1)溶液室温24h敏化。对电极的制备:采用丝网印刷方法,将一定浓度的H2PtCl6溶液印刷在FTO导电玻璃上,然后400℃马弗炉烧结20min。吸附染料的TiO2电极和铂对电极组装成三明治结构,并在边缘滴入电解质,利用毛细管渗透原理引入电池内部。于100mW/cm2光强照射下,测定光电压-电流特性曲线。其结果如表1和图1所示:
表1 苯并咔唑类化合物组装得到的DSSC性能参数
a:Jsc为短路电流密度;b:Ⅴoc为开路电压;c:ff为填充因子;d:η为光电转换效率。
由图1和表1可以看出,本发明所提供的染料敏化剂均具有光电转化能力,可以作为染料敏化太阳能电池的染料敏化剂,且其光电转化效率可达为5.10-7.67%,具有优异的光电转化性能。与参考如式(A)所示的化合物A(光电转换效率0.98%)[CN 104211691]相比,本发明报道的染料III光电转换效率大幅增长,效率增长;与如式(B)所示的类似参考化合物B和式(C)所示的化合物C[ACS Appl.Mater.Interfaces 2015,7,9015-9022]相比,本发明报道的化合物不仅结构进行了简化,染料II的光电转化效率也由B的6.93%增加到7.67%,染料III的光电转化效率由C的6.01%增加到6.58%。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
3.如权利要求2所述的苯并咔唑类化合物的制备方法,其特征在于氰基乙酸与式(Ⅳb)、式(Ⅳc)所示的化合物的投料摩尔比为2~4:1。
4.如权利要求2所述的苯并咔唑类化合物的制备方法,其特征在于哌啶与式(Ⅳb)、式(Ⅳc)所示的化合物的摩尔比为3~10:1。
5.如权利要求2所述的苯并咔唑类化合物的制备方法,其特征在于有机溶剂为氯仿、乙腈或四氢呋喃中的一种或多种。
6.如权利要求2所述的苯并咔唑类化合物的制备方法,其特征在于有机溶剂的体积用量以式(Ⅳb)、式(Ⅳc)所示的化合物的物质的量计为5~12mL/mmol。
7.如权利要求2所述的苯并咔唑类化合物的制备方法,其特征在于缩合反应的温度为60~80℃,反应时间为8~12h。
8.如权利要求7所述的苯并咔唑类化合物的制备方法,其特征在于反应混合液的后处理方法为:反应结束后,所得反应混合液蒸除溶剂后,残余物用洗脱溶剂进行硅胶柱层析,以二氯甲烷、甲醇及醋酸的混合溶液为洗脱剂,收集含目标化合物的洗脱液,浓缩干燥分别得式(Ⅱ)或式(Ⅲ)所示的苯并咔唑类化合物。
9.如权利要求8所述的苯并咔唑类化合物的制备方法,其特征在于洗脱溶剂为体积比为400:4:1的二氯甲烷、甲醇和醋酸的混合溶剂。
10.一种如权利要求1所述的苯并咔唑类化合物作为染料敏化剂在染料敏化太阳能电池中的应用。
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