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CN104311549B - 一种咔唑类染料敏化剂的合成及应用 - Google Patents

一种咔唑类染料敏化剂的合成及应用 Download PDF

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CN104311549B
CN104311549B CN201410511948.3A CN201410511948A CN104311549B CN 104311549 B CN104311549 B CN 104311549B CN 201410511948 A CN201410511948 A CN 201410511948A CN 104311549 B CN104311549 B CN 104311549B
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CN104311549A (zh
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韩亮
李婷
李郁锦
叶青
高建荣
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Zhejiang University of Technology ZJUT
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Abstract

本发明公开了一种咔唑类化合物及其制备与应用。所述咔唑类化合物如式（）、式（II）和式（III）所示；本发明所述的合成方法为：将式（IVa~IVc）化合物与式（V）与有机溶剂混合，在碱性化合物的作用下，加热回流搅拌反应1~10h，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）所示的咔唑类化合物；本发明所述的咔唑类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

一种咔唑类染料敏化剂的合成及应用
技术领域
本发明涉及一种咔唑类染料敏化剂的合成及应用。
背景技术
染料敏化太阳能电池（Dye Sensitized Solar Cell，DSSC）凭借其成本低、可弱光发电、光电转化率不受温度影响等特点，极有希望替代硅半导体光电转换部件，成为下一代实用型高性能太阳能电池。染料敏化剂是DSSC中决定可见光吸收和光电转换效率的关键结构材料，具有结构易设计修饰和加工、成本低、稳定性好等特点。
国内外染料敏化剂的研究主要分两类，一类为有机金属配合物，典型结构为功能性多吡啶钌化合物。这类染料敏化剂在可见光区吸收较强，氧化还原性能可逆，氧化稳定性高，但钌作为稀有金属成本较高，其染料吸收光谱窄。第二类为非金属有机染料，具有摩尔吸光系数高、吸收光谱宽和可通过结构修饰调变产生优良电化学性能等优点，是近年来染料敏化剂的研究热点。传统的非金属有机染料敏化剂的结构通式为“给体-π共轭桥-受体”(Donor-π Bridge-Acceptor，D-π-A)，根据给体的不同，已有香豆素型、吲哚啉型、三芳胺型等非金属染料敏化剂得以设计和开发。常用的受体为氰乙酸以及罗丹宁乙酸，而为了进一步增强受体与TiO2之间的键合能力，最近也有一些非羧酸受体的染料敏化剂被报道。
咔唑及其衍生物具有较好的吸收和发射光谱，较优的空穴传输能力和较宽的能级，被广泛应用于电致发光、非线性光学和光折射材料。同时咔唑作为一种优良的电子给体，被应用于染料敏化剂的设计开发中。Koumura团队设计合成了一系列以咔唑为电子给体，聚噻吩为桥键的新型D-π-A类敏化剂分子，光电转换效率最高达到8.3%。Wong课题组报道了以咔唑为给体的新型染料分子效率达到4.65%。本发明以原料易得的咔唑作为给体，4-苯基-2-噻吩-1,3-噻二唑作为桥键，氰乙酸作为受体，设计合成了三个咔唑类染料敏化剂。目前，尚无文献报道该结构的太阳能电池应用。
发明内容
本发明的目的在于提供一种咔唑类化合物的制备及将其应用于染料敏化太阳能电池。
本发明的结构式如下：
本发明所述如式（I）或式（II）或式（III）所示的咔唑类化合物可按照以下方法制备得到：将式（IVa~ IVc）化合物与式（V）与有机溶剂混合，在碱性化合物的作用下，加热回流搅拌反应1~10 h，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）或式（II）或式（III）所示的咔唑类化合物；所述有机溶剂为乙腈、氯仿、四氢呋喃或1,4-二氧六环中的一种或多种；所述碱性化合物为哌啶、吡啶、三乙胺或者二甲胺中的一种或多种；所述洗脱剂溶剂为氯仿、二氯甲烷和甲醇、乙醇及醋酸的混合溶剂；式（IV）化合物与式（V）化合物和碱性物质的物质的量之比为：1:1.0~3.0:0.1~0.3，有机溶剂体积用量以式（IV）化合物的物质的量计为3~10 mL/mmol。
所述有机溶剂为乙腈、氯仿、四氢呋喃或1,4-二氧六环中的一种或多种，优选乙腈和氯仿;
所述碱性化合物为哌啶、吡啶、三乙胺或者二甲胺中的一种或多种，优选哌啶；
所述的反应时间为1~10 h，优选为7 h;
所述洗脱剂溶剂为氯仿、二氯甲烷和甲醇、乙醇及醋酸的混合溶剂，优选为二氯甲烷、甲醇和醋酸的混合溶剂（v:v:v=400:8:2）;
所述有机溶剂用量以式（IV）化合物的物质的量计为3~10 mL/mmol，优选3 mL/mmol。
式（IVa）所示的化合物可按照以下方法制备得到： 将三氯氧磷加入N，N-二甲基甲酰胺冰浴下搅拌1小时后，将式(VIa)化合物溶于N，N-二甲基甲酰胺加入到上述体系中，N2保护下加热回流制备得到。
式（IVb~IVc）所示的化合物可按照以下方法制备得到：将三氯氧磷加入N，N-二甲基甲酰胺冰浴下搅拌1小时后，将式( VIb)或式( VIc)化合物溶于N，N-二甲基甲酰胺加入到上述体系中，N2保护下加热回流制备得到。
上述均为本领域技术人员公知的制备方法。
所述的咔唑类化合物作为染料敏化剂的应用，具体的应用如下：
将咔唑类化合物溶于CH3CN-DMSO（V:V=24:1）混合溶剂中，浸泡双层TiO2 纳米粒子膜光电极24 h。负载了咔唑类化合物的TiO2电极与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100 mW/cm2光强照射下，测定光电压-电流特性曲线。其结果表明此类咔唑类化合物的光电转换效率为2.01%-4.72%。
本发明制备的咔唑类化合物有益效果主要体现在：提供了一种新的咔唑类化合物，制备方法简单，该化合物作为染料敏化剂组装成的染料敏化太阳能电池具有较好的光电转换效率，为染料敏化剂的筛选增添了新的可应用物质。
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
VIa的合成
将VIII(0.09 g, 0.30 mmol )、咔唑VII(0.06 g, 0.36 mmol )、醋酸钯 (0.006g, 0.009 mmol )、四氟硼酸三叔丁基膦（0.09 g, 0.03 mmol）、碳酸铯（0.29 g, 0.90mmol）, 溶于二甲苯（3 mL），N2保护下回流 10 h，冷却至室温，旋干溶剂后，柱分离（PE）得米黄色固体(99 mg，收率80 %)。m.p.: 144-146 ºC; 1H NMR (500 MHz, CDCl3) δ: 8.22-8.17 (m, 4H, ArH), 7.67(d, J = 3.6 Hz, 2H, ArH), 7.62 (d, J = 3.6 Hz, 1H,ArH), 7.51-7.43 (m, 6H, ArH), 7.33 (t, J = 7.3 Hz, 2H, ArH), 7.14 (dd, J =4.8, 3.9 Hz, 1H, ArH); HREIMS m/z 409.0821 [M+H]+, cacld C25H16N2S2 for:408.0755.
IVa的合成
将三氯氧磷（0.20 mL, 0.60 mmol）加入N，N-二甲基甲酰胺（1mL）中，冰浴下搅拌1小时后，将式(VIa)化合物(0.20 g, 0.30mmol)溶于N，N-二甲基甲酰胺（2 mL）加入到上述体系中，N2保护下加热回流7h，冷却至室温，倒入大量冰水中，用CH2Cl2萃取三次，柱分离（PE:CH2Cl2=4:1）得到黄色固体 (58 mg，收率44 %)。m.p.: 193-195ºC; 1H NMR (500 MHz,CDCl3) δ: 10.16 (s, 1H, CHO), 8.19 (d, J=7.7 Hz, 2H, Ar-H), 8.05 (d, J=8.4Hz, 2H, ArH), 7.83-7.76 (m, 3H, ArH), 7.61 (dd, J = 5.0, 0.9 Hz, 1H, ArH),7.54 (d, J = 8.2 Hz, 2H, ArH), 7.49-7.45 (m, 2H, ArH), 7.37-7.32 (m, 2H,ArH), 7.20 (dd, J = 4.9, 3.9 Hz, 1H, ArH); HREIMS m/z 437.2096 [M+H]+, cacldC26H16N2OS2 for: 436.0704.
I的合成
IVa(2.62 g, 6 mmol)和氰基乙酸 V (1.27 g, 12 mmol) 溶于乙腈（5 mL）和氯仿（15mL）混合溶剂中，加入哌啶 (51mg, 0.6 mmol)，N2保护下回流7 h后，旋干溶剂，柱分离（HAc:MeOH:CH2Cl2=2:8:400）得到橘红色固体 (1.53 g，收率50 %)。m.p.: 273-275ºC;1H NMR (500 MHz, DMSO) δ: 8.37 (s, 1H, CH=CCN), 8.29 (d, J = 7.6 Hz, 2H,ArH), 8.01 (d, J = 7.7 Hz, 4H, ArH), 7.90 (d, J = 8.1 Hz, 2H, ArH), 7.50-7.44(m, 4H, ArH), 7.39-7.28 (m, 3H, ArH); 13C NMR (100 MHz, DMSO) δ: 164.01,163.41, 161.84, 140.45, 140.30 (2C), 138.69, 135.92, 132.39, 132.24, 132.07(2C), 130.54, 129.71, 128.36, 127.62, 127.31(2C), 126.88 (2C), 123.47 (2C),121.07 (2C), 120.89 (2C), 110.23 (2C), 100.03; HREIMS m/z 504.0839 [M+H]+,cacld C29H17N3O2S2 for: 503.0762.
实施例2
VIb的合成
取IX（3.30 g，10mmol）溶于重蒸的THF（50 mL），N2保护，-78℃下加入n-BuLi（2.5mol/L，5 mL，12 mmol），低温搅拌1h后加入硼酸三甲酯（4 mL，15 mmol），室温搅拌20 h，反应液不处理，直接与VIII（1.95 g，6 mmol），四（三苯基膦)钯(0.32 g，0.3 mmol)，碳酸钾溶液（2mol/L，15mL）的THF（30 mL）溶液混合，N2保护下加热回流14 h。加水和EA萃取，柱分离（PE:EA=30:1）得到白色固体（1.07 g，收率37%）。m.p.: 181-183ºC;1H NMR (500 MHz,CDCl3) δ: 8.43 (s, 1H, thiazole-H), 8.24 (d, J = 7.7 Hz, 1H, ArH), 8.09 (d, J= 8.4 Hz, 2H, ArH), 7.82 (d, J = 8.4 Hz, 2H, ArH), 7.73 (dd, J = 8.5, 1.8 Hz,1H, ArH), 7.67-7.59 (m, 5H, ArH), 7.51 (t, J = 7.7 Hz, 2H, ArH), 7.45 (t, J =5.6 Hz, 4H, ArH), 7.37-7.31 (m, 1H, ArH), 7.13 (dd, J = 5.0, 3.7 Hz, 1H,ArH); HREIMS m/z 485.1159 [M+H]+, cacld C31H20N2S2 for: 484.1068.
IVb的合成
将三氯氧磷（1 mL, 4 mmol）加入N，N-二甲基甲酰胺（4 mL）中，冰浴下搅拌1小时后，将式(VIb)化合物（0.97 g, 2 mmol）溶于N，N-二甲基甲酰胺（10 mL）加入到上述体系中，N2保护下加热回流7h，冷却至室温，倒入大量冰水中，用CH2Cl2萃取三次，柱分离（PE:CH2Cl2=4:1）得到黄色固体（404 mg，收率40 %）。m.p.: 308~311 ºC; 1H NMR (500 MHz,CDCl3) δ: 10.12 (s, 1H, CHO), 8.45 (s, 1H, thiazole-H), 8.24 (d, J = 7.7 Hz,1H, ArH), 7.99-7.87 (m, 4H, ArH), 7.78-7.72 (m, 2H, ArH),7.70-7.56 (m, 5H,ArH), 7.56-7.50 (m, 2H, ArH), 7.49-7.43 (m, 2H, ArH), 7.39-7.32 (m, 1H, ArH),7.19-7.17 (t, J = 4.7 Hz, 1H, ArH); ESI-MS:513 [M+H]+.
II 的合成
Ivb（0.27 g, 0.5 mmol）和氰基乙酸V（0.17 g, 1 mmol）溶于乙腈（1 mL）和氯仿（9 mL）混合溶剂中，加入哌啶(8.5 mg, 0.1 mmol)，N2保护下回流7 h后，旋干溶剂， 柱分离（HAc:MeOH:CH2Cl2=2:8:400）得到紫红色固体 (85 mg，收率30 %)。m.p.: 288-290ºC; 1HNMR (500 MHz, DMSO) δ: 8.75 (s, 1H, CH=CCN), 8.40 (d, J = 7.7 Hz, 1H, ArH),8.32 (s, 1H, thiazole-H), 8.05 (d, J = 8.2 Hz, 2H, ArH), 8.00 (dd, J=15.7,4.3 Hz, 2H, ArH), 7.88 (d, J=8.6 Hz, 1H, ArH), 7.81 (d, J = 8.2 Hz, 2H, ArH),7.72 (t, J = 7.7 Hz, 2H, ArH), 7.67 (d, J = 7.4 Hz, 2H, ArH), 7.58 (t, J =7.3 Hz, 1H, ArH), 7.51-7.45 (m, 2H, ArH), 7.41 (d, J = 8.2 Hz, 1H, ArH), 7.34(t, J = 7.4 Hz, 1H, ArH), 7.30 (t, J = 4.5 Hz, 1H, ArH); 13C NMR (100 MHz,DMSO) δ: 167.44, 165.15, 163.65, 142.96, 141.15, 140.53, 137.18, 135.86,132.82, 132.05, 132.22, 131.60, 131.29, 131.02 (3C), 130.71 (2C), 129.80,129.19, 128.29, 127.48 (2C), 127.14 (2C), 125.78, 125.06, 124.01, 123.38,121.42, 120.85, 119.52, 116.63, 110.63, 110.23; HREIMS m/z 580.1144 [M+H]+,cacld C35H21N3O2S2 for: 579.1075.
实施例3
VIc的合成
取XI（3.20 g，10 mmol）溶于重蒸的THF（50 mL），N2保护，-78℃下加入n-BuLi(2.5mol/L，5 mL，12mmol)，低温搅拌1h后加入硼酸三甲酯（4 mL，15mmol），室温搅拌20 h，反应液不处理，直接与VIII（1.97 g，6 mmol），四（三苯基膦)钯 (0.33 g，0.3 mmol)，碳酸钾溶液（2mol/L，15 mL）的THF（30mL）溶液混合，N2保护下加热回流14 h。加水和EA萃取，柱分离（PE:EA=30:1）得到白色固体（0.77 g，收率30%）。m.p.: 138-140 ºC; 1H NMR (500MHz, CDCl3) δ: 8.39 (d, 1H, thiazole-H), 8.20 (d, J = 7.7 Hz, 1H, ArH), 8.08(d, J = 8.3 Hz, 2H, ArH), 7.82 (d, J = 8.3 Hz, 2H, ArH), 7.79 (dd, J = 8.5,1.7 Hz, 1H, ArH), 7.60 (dd, J = 3.6, 0.9 Hz, 1H, ArH), 7.53-7.49 (m, 2H,ArH), 7.46-7.44 (m, 3H, ArH), 7.28 (t, J = 3.5 Hz, 1H, ArH), 7.13 (dd, J =5.0, 3.7 Hz, 1H, ArH), 4.36 (t, J = 7.2 Hz, 2H, CH 2CH2CH2CH3), 1.97-1.85 (m,2H, CH2CH 2CH2CH3), 1.51-1.39 (m, 2H, CH2CH2CH 2CH3), 0.99 (t, J = 7.4 Hz, 3H,CH2CH2CH2CH 3); HREIMS m/z 465.1457 [M+H]+, cacld C29H24N2S2 for: 464.1381.
IVc的合成
将三氯氧磷（0.5 mL, 2 mmol）加入N，N-二甲基甲酰胺(2 mL)中，冰浴下搅拌1小时后，将式(VIc)化合物（0.48 g, 1 mmol）溶于N，N-二甲基甲酰胺（8 mL）加入到上述体系中，N2保护下加热回流7h，冷却至室温，倒入大量冰水中，用CH2Cl2萃取三次，柱分离（PE:CH2Cl2=4:1）得到黄色固体（162mg，收率33 %）。m.p.: 164-166ºC;1H NMR (500 MHz,CDCl3) δ: 10.12 (s, 1H, CHO), 8.40 (s, 1H, thiazole-H), 8.19 (d, J = 7.7 Hz,1H, ArH), 7.92-7.89 (m, 4H, ArH), 7.79 (dd, J = 8.5, 1.7 Hz, 1H, ArH), 7.75(dd, J = 3.7, 0.9 Hz, 1H, ArH), 7.58 (dd, J = 5.0, 1.0 Hz, 1H, ArH), 7.52 (t,J = 8.4 Hz, 2H, ArH), 7.46 (d, J = 8.2 Hz, 1H, ArH), 7.30 (d, J = 7.7 Hz, 1H,ArH), 7.18 (dd, J = 4.9, 3.8 Hz, 1H, ArH), 4.37 (t, J = 7.2 Hz, 2H,CH 2CH2CH2CH3), 1.95-1.89 (m, 2H, CH2CH 2CH2CH3), 1.49-1.42 (m, 2H, CH2CH2CH 2CH3),0.99 (t, J = 7.4 Hz, 3H, CH2CH2CH2CH 3); HREIMS m/z 493.1504 [M+H]+, cacldC30H24N2OS2 for: 492.1330.
III的合成
IVc（0.13 g, 0.30 mmol）和氰基乙酸V（0.08 g, 0.60 mmol）溶于乙腈（1 mL）和氯仿（2 mL）混合溶剂中，加入哌啶(2.5 mg, 0.03 mmol)，N2保护下回流7 h后，旋干溶剂，柱分离（HAc:MeOH:CH2Cl2=2:8:400）得到红色固体 (93 mg，收率55 %)。m.p.: 274-276ºC;1H NMR (500 MHz, DMSO) δ: 8.65 (s, 1H, CH=CCN), 8.33 (s, 1H, thiazole-H),8.30 (d, J = 7.7 Hz, 1H, ArH), 8.04 (d, J = 8.3 Hz, 2H, ArH), 8.01 (d, J =3.7 Hz, 1H, ArH), 7.98 (d, J = 5.0 Hz, 1H, ArH), 7.90 (d, J = 8.6 Hz, 1H,ArH), 7.80 (d, J = 8.3 Hz, 2H, ArH), 7.72 (d, J = 8.6 Hz, 1H, ArH), 7.64 (d,J = 8.3 Hz, 1H, ArH), 7.49 (t, J = 7.6 Hz, 1H, ArH), 7.30 (dd, J = 4.9, 3.9Hz, 1H, ArH), 7.24 (t, J = 7.3 Hz, 1H, ArH), 4.44 (t, J = 7.0 Hz, 2H,CH 2CH2CH2CH3), 1.82-1.76 (m, 2H, CH2CH 2CH2CH3), 1.37-1.29 (m, 2H, CH2CH2CH 2CH3),0.90 (t, J = 7.4 Hz, 3H, CH2CH2CH2CH 3); 13C NMR (100 MHz, DMSO) δ: 165.26,164.61, 163.74, 144.67, 143.32, 141.01, 140.45, 135.82, 132.90, 131.01 (3C),130.17, 129.84, 127.42 (3C,), 126.49, 125.22, 125.01, 124.92, 123.29, 122.73,121.15, 119.43, 119.24, 116.61, 110.32, 109.97, 42.74, 31.22, 20.28, 14.22;HREIMS m/z 560.1467 [M+H]+, cacld C33H25N3O2S2 for: 559.1388.
实施例4
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 12 μm 厚的 20 nm 的TiO2粒子， 450 ºC下马弗炉内煅烧 30 min。在浸染料之前将烧好的膜浸入 0.04 mol·L-1 的TiCl4 水溶液 70 ºC 预处理 30 min， 然后分别用水和乙醇冲洗，电吹风吹干。经马弗炉450 ºC下再次煅烧 30 min 后，冷却至 80 ºC 后浸入3×10-4 mol·L-1 染料的乙腈与 DMSO 溶液室温 24 h 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 ºC马弗炉烧结 20 min。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（含0.07 mM/LI-），利用毛细管渗透原理引入电池内部。于100 mW/cm2光强照射下，测定光电压-电流特性曲线。其结果如表1所示：
表 1咔唑敏化剂组装得到的DSSC性能参数
Compd Jsc (mA·cm-2) Voc (mV) ff η %
I 5.15 0.58 0.68 2.01
II 10.01 0.66 0.72 4.72
III 9.68 0.65 0.71 4.47

Claims (3)

1.一种结构如式II所示的咔唑类化合物，
。
2.制备权利要求1 所述的咔唑类化合物的方法，其包括如下步骤：将式IVb化合物与式V与有机溶剂混合，在碱性化合物的作用下，加热回流搅拌反应1~10 h，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II所示的咔唑类化合物；
所述碱性化合物为哌啶、吡啶、三乙胺或者二甲胺中的一种或多种；所述有机溶剂为乙腈、氯仿、四氢呋喃或1,4-二氧六环中的一种或多种；
所述洗脱剂溶剂为氯仿、二氯甲烷和甲醇、乙醇及醋酸的混合溶剂；
式IVb化合物与式V化合物和碱性物质的物质的量之比为 1:1.0~3.0: 0.1~0.3，有机溶剂体积用量以式IVb化合物的物质的量计为10~30 mL/mmol，
和。
3.一种如权利要求1所述的咔唑类化合物在太阳能电池上的应用。
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