CN115340665A - 两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物及其制备方法与用途 - Google Patents
两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物及其制备方法与用途 Download PDFInfo
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Abstract
本发明涉及式1所示两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT‑BBT‑Hg、BDTT‑BBT‑Cd及其制备方法与用作染料敏化太阳能电池中染料敏化剂的用途,该类共聚聚合配合物染料敏化剂以苯并二噻吩衍生物BDTT为电子给体D,以2,7‑二溴‑4,5‑二丁氧基‑[2,1‑b:3,4‑b']‑二噻吩与金属配位形成的配合物作为辅助电子受体A’,以2‑氰基‑3‑(8‑羟基喹啉‑5‑基)丙烯酸作为π桥和锚定基团,通过Yamamoto偶联反应合成的D‑A’‑π‑A型共聚聚合配合物,实验基于该类共聚聚合配合物染料敏化剂的染料敏化太阳能电池的光伏性能测试表现出较好的效果:光电转换效率分别为11.77%、10.32%,其热分解温度均在270℃以上,热稳定性良好,这将在染料敏化太阳能电池的发展应用方面具有一定的前景。
Description
技术领域
本发明涉及两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd及其制备方法与用作染料敏化剂的用途,是对染料敏化太阳能电池(DSSCs)中光电敏化材料的研发与应用,属于新材料中的光电材料领域。
背景技术
近年来,对于染料敏化太阳能电池的重要组成部分—染料敏化剂的研究取得了重大进展,有研究人员发现在D-π-A结构的基础上引入辅助电子受体A’,可以使光电转化效率得到明显提升,同时对染料敏化剂的热稳定性能也有较明显改善;现阶段常用一些有机化合物作为辅助电子受体A’,但其吸电子的能力有限、共轭平面结构性也不够,而金属配合物拥有较好的吸电子能力,并能通过引入不同的金属原子来调节吸电子能力,以达到染料分子优良的推拉电子平衡,因而本发明研究以丁氧基苯并二噻吩衍生物合金属共聚配合物代替有机化合物作辅助受体A’,并通过聚合扩大分子共轭平面性,设计与制备了两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd,测试数据表明它们具有较好的吸光性能与光伏性能。
发明内容
本发明的目的为提供和制备两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd,以用作染料敏化太阳能电池中的D-A’-π-A型染料敏化剂;该染料敏化剂以苯并二噻吩衍生物BDTT为电子给体D,以苯并二噻吩类衍生物与金属配位构成主配体A’,以2-氰基-3-(8-羟基喹啉-5-基)丙烯酸作为π桥和锚定基团,通过Yamamoto偶联反应将电子给体D和电子吸体部分(-A’-π-A)聚合形成两种聚合配合物染料敏化剂,该类聚合配合物具有良好的光电转换效率和热稳定性,基于以上两种配合物作为染料敏化剂的染料敏化太阳能电池的光电转化效率依次为11.77%、10.32%,其结构通式如下:
两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd的制备方法:
(1)1,2-二噻吩-1,2-二酮的制备:
将噻吩-3-甲醛与K2CO3按摩尔比为1.0∶1.2~1.0∶1.8加入至单口烧瓶中后,接着将DMSO和3-苄基-5-(2-羟乙基)-4-甲基噻唑鎓溴化物加入,然后在二氧化碳的气氛下,加热回流34~38h,反应完成后冷却至室温,接着加入水中,并用乙醚萃取三次,然后加入无水硫酸镁进行干燥,过滤后旋干得到淡黄色液体,所得粗产物用体积比为1∶10~1∶15的乙酸乙酯与石油醚的混合溶液做洗脱剂进行过柱分离,得到金黄色针状固体1,2-二噻吩-1,2-二酮;
(2)苯并[1,2-b:6,5-b']二噻吩-4,5-二酮的制备:
将二氯甲烷和1,2-二噻吩-1,2-二酮加入至单口烧瓶中并搅拌溶解,然后缓慢加入FeCl3,并在45℃下反应22~26h,反应完成后静置1~2h,加入去离子水,用二氯甲烷萃取三次,收集有机相并用无水硫酸镁干燥,过滤后旋干得到黑色絮状固体,所得粗产物用体积比为1∶10~1∶15的乙酸乙酯与石油醚的混合溶液做洗脱剂进行过柱分离,得到黑色针状固体苯并[1,2-b:6,5-b']二噻吩-4,5-二酮;
(3)2,7-二溴苯并[1,2-b:6,5-b']二噻吩-4,5-二酮的制备:
将苯并[1,2-b:6,5-b']二噻吩-4,5-二酮和NBS按摩尔比为1.0∶1.8~1.0∶2.4加入至单口烧瓶中,再加入DMF,接着在70℃下反应22~26h,反应完成后冷却至室温,倒入水中静置30~60min,抽滤后干燥,得到淡蓝色固体2,7-二溴苯并[1,2-b:6,5-b']二噻吩-4,5-二酮;
(4)2,7-二溴-4,5-二丁氧基-[2,1-b:3,4-b']-二噻吩的制备:
将摩尔比为1.0:1.0:0.6:6.2~1.0:1.1:0.7:6.5的2,7-二溴苯并[1,2-b:6,5-b']二噻吩-4,5-二酮、正溴丁烷、四丁基溴化铵和保险粉加入三口烧瓶中,接着加入四氢呋喃水溶液,并在氮气的保护下通过恒压滴液漏斗缓慢滴加KOH水溶液,滴加完成后,在80℃下反应46~50h,反应完成后冷却至室温,用乙酸乙酯萃取,收集有机相并用无水硫酸镁干燥,过滤后旋干得到淡黄色液体粗产物,所得粗产物用体积比1∶35~1∶45的乙酸乙酯、石油醚的混合溶液做洗脱剂进行过柱分离,得到黄色液体产物2,7-二溴-4,5-二丁氧基-[2,1-b:3,4-b']-二噻吩;
(5)5-甲酰-8-羟基喹啉的制备:
向三颈烧瓶中加入8-羟基喹啉、无水乙醇,在搅拌状态下通过恒压分液漏斗加入氢氧化钠溶液,完全溶解后加热至80℃回流,再通过恒压分液漏斗缓慢加入氯仿,8-羟基喹啉与氯仿的摩尔比为1.0∶2.0~1.0∶2.4,反应22~26h,反应完成后,减压蒸馏除去乙醇和氯仿,再倒入蒸馏水,用稀盐酸中和至pH为7.0,抽滤得到棕色固体,真空干燥后得到棕色块状物体,研磨至粉末状后继续干燥,再用石油醚洗涤,洗涤液冷却,再过滤上清液以后剩下的固体用无水乙醇重结晶两次,干燥得到橙粉色细丝状晶体5-甲酰基-8-羟基喹啉;
(6)2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的制备:
在三颈烧瓶中加入摩尔比为1.0∶1.2~1.0∶1.8的5-甲酰基-8-羟基喹啉和氰基乙酸,再加入乙酸、乙腈,搅拌至溶解,溶解后加入哌啶,接着在90℃下反应34~38h,反应完成后,旋干溶剂并干燥,将固体研磨至粉末状后用三氯甲烷洗涤三次,再将固体干燥以后用乙醇重结晶两次,得到橘色粉末2-氰基-3-(8-羟基喹啉-5-基)丙烯酸;
(7)金属配合物BBT-Hg的制备:
取摩尔比为1.0:1.0~1.0:1.2的2,7-二溴-4,5-二丁氧基-[2,1-b:3,4-b']-二噻吩和2-氰基-3-(8-羟基喹啉-5-基)丙烯酸,依次加入单口瓶内,加热溶解,然后将HgCl2溶于无水甲醇中,并通过恒压漏斗缓慢滴加,并在75℃下反应22~26h,反应完成后冷却至室温,放入冰箱中过夜使固体完全析出,并在过滤后分别用水洗涤三次,无水乙醇洗涤三次,最终得到淡黄色固体含Hg配合物BBT-Hg;
(8)金属配合物BBT-Cd的制备:
配合物BBT-Cd的合成方法与配合物BBT-Hg的合成方法一致,将反应所需的HgCl2换成Cd(CH3COO)2·2H2O,合成后得到金黄色固体含镉配合物BBT-Cd;
(9)聚合金属配合物BDTT-BBT-Hg的制备:
取摩尔比为1.0:0.8~1.0:1.2的配合物单体BBT-Hg和2,6-二溴-4,8-二(5-(2-乙基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩BDTT加入单口烧瓶中,然后再加入锌粉、三苯基磷、双(三苯基膦)二氯化镍以及2,2’-联吡啶,再加入DMF,接着根据Yamamoto聚合反应,在氮气保护下,回流反应46~50h,反应结束后,冷却、过滤,用无水乙醇洗涤并干燥,得到深棕色固体产物BDTT-BBT-Hg;
(10)聚合金属配合物BDTT-BBT-Cd的合成;
聚合物BDTT-BBT-Cd的合成方法参照BDTT-BBT-Hg的合成,将反应需要的汞金属配合物BBT-Hg改为金属配合物BBT-Cd,合成后得到淡棕色固体粉末聚合配合物BDTT-BBT-Cd;
两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd的用途:在染料敏化太阳能电池中用作吸收太阳光并产生与传输电子的染料敏化剂;
此发明的主要优势在于:(1)发明了两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd,它们以苯并二噻吩联二噻吩衍生物BDTT为给体(D),以2,7-二溴-4,5-二丁氧基-[2,1-b:3,4-b']-二噻吩与两种金属配位后形成的配合物作为辅助受体A’,以2-氰基-3-(8-羟基喹啉-5-基)丙烯酸作为π桥和锚定基团,通过Yamamoto反应将给体(D)和配合物受体部分-A’-π-A连接而合成的染料敏化剂,该类光敏剂表现出优良的光伏性能和光电转化效率,光电转换效率分别为11.77%、10.32%;(2)具有良好的电化学性能、热性能和光稳定性,热分解温度均在270℃以上,有利于实际应用。
附图说明
图1本发明实施例合成的配体1,2-二噻吩-1,2-二酮的核磁共振氢谱(1H-NMR)(400MHz,CDCl3,ppm);
图2本发明实施例合成的配体苯并[1,2-b:6,5-b']二噻吩-4,5-二酮的核磁共振氢谱(1H-NMR)(400MHz,CDCl3,ppm);
图3本发明实施例合成的配体2,7-二溴苯并[1,2-b:6,5-b']二噻吩-4,5-二酮的合成的核磁共振氢谱(1HNMR)(400MHz,CDCl3,ppm);
图4本发明实施例合成的配体2,7-二溴-4,5-二丁氧基-[2,1-b:3,4-b']-二噻吩的核磁共振氢谱(1HNMR)(400MHz,CDCl3,ppm);
图5本发明实施例合成的配体5-甲酰-8-羟基喹啉的核磁共振氢谱(1HNMR)(400MHz,CDCl3,ppm);
图6本发明实施例合成的配体2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的核磁共振氢谱(1HNMR)(400MHz,CDCl3,ppm);
图7本发明实施例合成的金属配合物BBT-Hg和BBT-Cd的红外光谱(FTIR)(KBr,cm-1);
图8本发明实施例合成的聚合配合物BDTT-BBT-Hg和BDTT-BBT-Cd的红外光谱(FT-IR)(KBr,cm-1);
图9本发明实施例合成的聚合配合物BDTT-BBT-Hg和BDTT-BBT-Cd的热重分析曲线(TGA)(N2,20℃/min);
图10本发明实施例合成的聚合配合物BDTT-BBT-Hg和BDTT-BBT-Cd作染料敏化剂的染料敏化太阳能电池的电流密度-电压(J-V)曲线;
图11本发明实施例合成的聚合配合物BDTT-BBT-Hg和BDTT-BBT-Cd的外量子效率(IPCE)曲线。
具体实施方式
本发明的两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd的反应合成路线如式1所示:
下面结合具体实施例对本发明做进一步的说明:
实施例1:
两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd,其分子结构式如式2所示:
式1两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物的合成路线
实施例2:
上述两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd的制备:
A.1,2-二噻吩-1,2-二酮的制备:将噻吩-3-甲醛3.6g(30mmol),K2CO3 6.18g(45mmol),16mL DMSO和3-苄基-5-(2-羟乙基)-4-甲基噻唑鎓溴化物0.153g(30mol)加入至50mL的单口烧瓶中,在二氧化碳的气氛中升温至60℃反应36h,反应完成后冷却至室温,加入100mL水,用50mL无水乙醚萃取三次后收集有机相,加入无水硫酸镁干燥12h,过滤旋干得到淡黄色液体粗产物,所得粗产物干燥完全后用体积比1∶12的乙酸乙酯、石油醚的混合溶液做洗脱剂进行过柱分离,得到金黄色针状固体1.62g,产率73%,m.p.94.1-94.7℃;FT-IR(KBr,cm-1):3440cm-1(-OH),3110cm-1(=C-H),1680cm-1(C=O),1160cm-1(C-C),1500cm-1(C=C),1100cm-1(C-S),700cm-1(=C-H);核磁共振氢谱(1H-NMR)见附图11H-NMR(CDCl3,ppm):8.35-8.36(d,1H),7.69-7.71(d,1H),7.39-7.41(q,1H);13C-NMR(CDCl3,ppm):186.81,137.59,137.50,127.54,126.96;
式2两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物的结构式
B.苯并[1,2-b:6,5-b']二噻吩-4,5-二酮的制备:将150mL二氯甲烷和1,2-二噻吩-1,2-二酮2.22g(10mmol)加入至250mL的单口烧瓶中并搅拌5min,然后缓慢加入FeCl38.1g(50mmol),在45℃下24h,反应完成后静置1h,加入300ml水,并用二氯甲烷萃取三次,收集有机相并用无水硫酸镁干燥24h,过滤后旋干得到黑色絮状固体,所得粗产物用体积比1∶12的乙酸乙酯、石油醚的混合溶液做洗脱剂进行过柱分离,得到黑色针状固体1.76g,产率为80%,m.p.289.1-289.6℃;FT-IR(KBr,cm-1):3090cm-1(=C-H),2930cm-1,2850cm-1,1390cm-1,1280cm-1(-C-H),1660(C=O),1510cm-1(C=C),1100cm-1(C-S),885cm-1(C-C),727cm-1(=C-H);核磁共振氢谱(1H-NMR)见附图2,1H-NMR(CDCl3,ppm):7.50(d,1H,=CH),7.20(d,1H,=CH);13C-NMR(CDCl3,ppm):174.62,143.96,135.11,127.88,125.66;
C.2,7-二溴苯并[1,2-b:6,5-b']二噻吩-4,5-二酮的制备:将苯并[1,2-b:6,5-b']二噻吩-4,5-二酮4.40g(20mmol),NBS 3.738g(42mmol)和100mL DMF加入到250mL单口烧瓶中,升温至70℃反应24h,反应完成后冷却至室温,倒入400mL水中静置30min使得固体完全析出,抽滤后干燥48h,得到淡蓝色固体2.85g,产率为75.3%,m.p.204.3-204.9℃;FT-IR(KBr,cm-1):3450cm-1(-OH),30110cm-1(=CH),2930cm-1,2850cm-1,1410cm-1,1280cm-1(-C-H),1680cm-1(C=O),1510cm-1(C=C),1080cm-1(C-S),629cm-1(C-Br);核磁共振氢谱(1H-NMR)见附图3,1H-NMR(CDCl3,ppm):7.47(s,1H,=CH);13C-NMR(CDCl3,ppm):172.57,143.63,135.37,130.03,114.65;
D.2,7-二溴-4,5-二丁氧基-[2,1-b:3,4-b']-二噻吩的制备:将1.50g2,7-二溴苯并[1,2-b:6,5-b']二噻吩-4,5-二酮(4mmol),0.58g正溴丁烷(4.2mmol),0.87g四丁基溴化铵(2.7mmol),4.44g保险粉(25.5mmol)加入至100mL的三口烧瓶中,再加入20mL四氢呋喃与10mL水的混合溶液,在氮气的保护下通过恒压滴液漏斗缓慢滴加KOH水溶液(2.31g/10mL),滴加完成后缓慢升温至80℃反应48h,反应完成后冷却至室温,用30mL乙酸乙酯萃取三次,收集有机相并用无水硫酸镁干燥过夜,过滤旋干后得到淡黄色液体粗产物,柱层析法过柱处理,以石油醚和乙酸乙酯为洗脱剂,石油醚和乙酸乙酯的比例为40:1(v/v),得到黄色液体产物0.84g,产率为43%,核磁共振氢谱(1H-NMR)见附图4,1H-NMR(CDCl3,ppm):7.43(s,1H),4.10-4.13(t,2H),1.76-1.80(t,2H),1.55-1.50(q,2H),1.01-0.97(t,3H).13C-NMR(CDCl3,ppm):142.78,134.15,129.02,124.66,112.84,74.13,32.42,19.43,13.97.FT-IR(KBr,cm-1):3440(-OH),3090(=CH),2960,1380(-CH3),2930,2850(C-H),1460(-CH2),1280,1060(=C-O-C);
E.5-甲酰基-8-羟基喹啉的制备;在一500ml的三颈烧瓶依次加入20g(137.6mmol)的8-羟基喹啉,再加入80ml的无水乙醇后再在搅拌状态下通过恒压分液漏斗缓慢加入质量比为1:1的氢氧化钠水溶液(NaOH 40g,H2O 40mL),体系完全溶解以后加热至80℃回流,再通过恒压分液漏斗在1h缓慢加入36g(304mmol)CHCl3,滴加完毕以后再反应24h;反应毕,加入50ml的蒸馏水后再将溶剂通过减压蒸馏除去,旋干以后再用稀盐酸(盐酸:水=10:1)中和至pH为7,此时出现大量棕色固体;抽滤、真空干燥后得到棕色块状物体,固体研磨至粉末状后继续干燥,干燥完全以后再用石油醚洗涤,将洗涤液自然冷却,析出橙色固体,过滤上清液固体用无水酒精重结晶两次,得到的固体彻底干燥后得到橙粉色细丝状晶体3.0g,产率为12.3%,m.p.171.8~172.9℃;FT-IR(KBr,cm-1):3447cm-1(-OH),2920cm-1(C-H),1690cm-1(C=O),1576cm-1(C=C),1510cm-1(C=N);核磁共振氢谱(1H-NMR)见附图5,1H-NMR(CDCl3,ppm):10.15(s,1H),9.67(d,1H),8,87(d,1H),8.00(d,1H),7.67(q,1H),7.65(d,1H);13C-NMR(CDCl3,ppm):192.04,157.86,148.74,140.45,137.85,134.76,126.59,124.72,123.56,109.02;
F.2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的制备:在一500ml的三颈烧瓶依次加入3.0g(17.3mmol)5-甲酰基-8-羟基喹啉、2.22g(26.0mmol)氰基乙酸后,再加入9ml的乙酸、随后加入100ml乙腈,搅拌至溶解,溶解以后缓慢加入1ml的哌啶,将体系于90℃下反应36h,反应毕,旋干溶剂以后置于真空干燥箱直至干燥完全,得到黄色块状的粗产物,将粗产物研磨至粉末状后用三氯甲烷洗涤固体三次,再将固体干燥以后用乙醇重结晶两次,得到橘色粉末固体2.0g,产率为59.1%,m.p.200~201℃;核磁共振氢谱(1H-NMR)见附图6,1H-NMR(DMSO-d6,ppm):8.96(s,1H),8.87(d,1H),8.62(d,1H),8.42(d,1H),7.71(q,1H),7.26(d,1H).羟基和羧基上的活泼氢因形成氢键而无法在核磁氢谱中表征出,但可结合FT-IR和13C-NMR表征证明目标产物成功合成,结果如下:FT-IR(KBr,cm-1):3180cm-1(-OH),2235cm-1(C≡N),1896cm-1(C=O),1662cm-1(C=O),1613cm-1(C=C),1566cm-1(C=N);13C-NMR(CDCl3,ppm):164.17,159.12,150.04,149.44,138.68,132.58,131.15,128.71,123.93,118.86,117.26,112.16,102.93.
G.含Hg配合物BBT-Hg的制备:在50mL的单口烧瓶中依次加入2,7-二溴-4,5-二丁氧基-[2,1-b:3,4-b']-二噻吩0.25g(0.5mmol),2-氰基-3-(8-羟基喹啉-5-基)丙烯酸0.12g(0.55mmol),25mL THF升温至40℃溶解,然后将0.149g HgCl2(0.55mmol)溶于20mL无水甲醇中,并通过恒压漏斗缓慢滴加,升温至75℃反应24h,反应完成后冷却至室温,放入冰箱中过夜使固体完全析出,过滤后分别用水洗涤三次,无水乙醇洗涤三次,最终得到淡黄色固体0.274g,产率为56.8%;红外谱图(FT-IR)(KBr,cm-1)见附图7,FT-IR(KBr,cm-1):3440(-OH),2935,2851(C-H),2210(C≡N),1618(C=C),1560(C=N),1102(S-O-Hg),492,(S-Hg);
H.含Cd配合物BBT-Cd的制备:配合物Cd的合成方法与配合物BBT-Hg的合成方法一致,将HgCl2改为0.134g(0.55mmol)Cd(CH3COO)2·2H2O,经与之相同的后处理后得到金黄色固体0.264g,产率为58.5%;红外谱图(FT-IR)(KBr,cm-1)见附图7,FTIR(KBr,cm-1):3443(-OH),2933,2850(C-H),2209(C≡N),1617(C=C),1558(C=N),1105(S-O-Cd),496(S-Cd);
I.聚合金属配合物BDTT-BBT-Hg的合成:在一50ml的单口烧瓶中依次加入Hg配合物BBT-Hg 0.225g(0.25mmol)以及2,6-二溴-4,8-二(5-(2-乙基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩(BDTT)给体单体0.184g(0.25mmol),锌粉0.08g(1.25mmol),三苯基磷0.13g(0.5mmol),双(三苯基膦)二氯化镍0.16g(0.25mmol)以及2,2’-联吡啶0.004g(0.024mmol),再加入15mL DMF,在氮气保护下回流反应48h;反应结束后过滤,用无水乙醇充分洗涤并干燥得深棕色固体产物0.205g,产率48.3%;红外谱图(FT-IR)(KBr,cm-1)见附图8,FTIR(KBr,cm-1):3437(-OH),2932,2850(C-H),2208(C≡N),1615(C=C),1558(C=N),1100(S-O-Hg),489(S-Hg).Mn=8.46×103g/mol,PDI=2.07;
J.聚合金属配合物BDTT-BBT-Cd的合成:聚合物BDTT-BBT-Cd的合成方法参照BDTT-BBT-Hg的合成,将反应需要的Hg配合物BBT-Hg换成铜配合物BBT-Cd 0.225g(0.30mmol),然后在相同条件下与给体BDTT 0.184g(0.25mmol)反应,经过相同的处理以后得到淡棕色固体粉末0.211g,产率为51.3%;红外谱图(FT-IR)(KBr,cm-1)见附图8,FTIR(KBr,cm-1):3440(-OH),2931,2848(C-H),2207(C≡N),1613(C=C),1556(C=N),1102(S-O-Cd),493(S-Cd).Mn=9.33×103g/mol,PDI=2.11。
实施例3:
测定两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd的热重分析(TGA)曲线,方法:SDTQ600的热重分析仪,在N2保护下以20℃/min的升温速度进行测试,测试结果如图9。
实施例4:
测定两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd的分子量,方法为凝胶渗透色谱(GPC):使用Waters-1515型号的凝胶渗透色谱仪,分离柱为waters styragel columns(103,104,),柱温箱温度80℃,以DMF为流动相,聚苯乙烯溶液作参比,流速为1.00mL/min进行测试,测试结果如表1:
表1两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物的分子量测试结果
实施例5:
两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd的光伏性能测试:电流密度-电压(J-V)曲线测试光源为氙灯模拟的光强100mW/cm2的AM 1.5G的太阳光,通过Keithley 2400数字源表改变电压并记录电流随电压的变化值;外量子效率(IPCE)测试由Oriel Cornerstone单色仪提供光源,在短路条件下测得,波长的测试间隔为10nm,DSSCs的有效工作面积为0.25cm2;测定以两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd为染料敏化剂的染料敏化太阳能电池的性能参数和光电转换效率,其电池电流密度-电压(J-V)曲线如图10,电池外量子效率(IPCE)曲线如图11;表2是它们的光伏性能和光电转换效率测试结果。
表2两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物的光伏性能测试结果
Claims (2)
1.两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd,其结构式如下:
如上述的两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd的制备方法:
(1)1,2-二噻吩-1,2-二酮的制备:
将噻吩-3-甲醛与K2CO3按摩尔比为1.0∶1.2~1.0∶1.8加入至单口烧瓶中后,接着将DMSO和3-苄基-5-(2-羟乙基)-4-甲基噻唑鎓溴化物加入,然后在二氧化碳的气氛下,加热回流34~38h,反应完成后冷却至室温,接着加入水中,并用乙醚萃取三次,然后加入无水硫酸镁进行干燥,过滤后旋干得到淡黄色液体,所得粗产物用体积比为1∶10~1∶15的乙酸乙酯与石油醚的混合溶液做洗脱剂进行过柱分离,得到金黄色针状固体1,2-二噻吩-1,2-二酮;
(2)苯并[1,2-b:6,5-b']二噻吩-4,5-二酮的制备:
将二氯甲烷和1,2-二噻吩-1,2-二酮加入至单口烧瓶中并搅拌溶解,然后缓慢加入FeCl3,并在45℃下反应22~26h,反应完成后静置1~2h,加入去离子水,用二氯甲烷萃取三次,收集有机相并用无水硫酸镁干燥,过滤后旋干得到黑色絮状固体,所得粗产物用体积比为1∶10~1∶15的乙酸乙酯与石油醚的混合溶液做洗脱剂进行过柱分离,得到黑色针状固体苯并[1,2-b:6,5-b']二噻吩-4,5-二酮;
(3)2,7-二溴苯并[1,2-b:6,5-b']二噻吩-4,5-二酮的制备:
将苯并[1,2-b:6,5-b']二噻吩-4,5-二酮和NBS按摩尔比为1.0∶1.8~1.0∶2.4加入至单口烧瓶中,再加入DMF,接着在70℃下反应22~26h,反应完成后冷却至室温,倒入水中静置30~60min,抽滤后干燥,得到淡蓝色固体2,7-二溴苯并[1,2-b:6,5-b']二噻吩-4,5-二酮;
(4)2,7-二溴-4,5-二丁氧基-[2,1-b:3,4-b']-二噻吩的制备:
将摩尔比为1.0:1.0:0.6:6.2~1.0:1.1:0.7:6.5的2,7-二溴苯并[1,2-b:6,5-b']二噻吩-4,5-二酮、正溴丁烷、四丁基溴化铵和保险粉加入三口烧瓶中,接着加入四氢呋喃水溶液,并在氮气的保护下通过恒压滴液漏斗缓慢滴加KOH水溶液,滴加完成后,在80℃下反应46~50h,反应完成后冷却至室温,用乙酸乙酯萃取,收集有机相并用无水硫酸镁干燥,过滤后旋干得到淡黄色液体粗产物,所得粗产物用体积比1∶35~1∶45的乙酸乙酯、石油醚的混合溶液做洗脱剂进行过柱分离,得到黄色液体产物2,7-二溴-4,5-二丁氧基-[2,1-b:3,4-b']-二噻吩;
(5)5-甲酰-8-羟基喹啉的制备:
向三颈烧瓶中加入8-羟基喹啉、无水乙醇,在搅拌状态下通过恒压分液漏斗加入氢氧化钠溶液,完全溶解后加热至80℃回流,再通过恒压分液漏斗缓慢加入氯仿,8-羟基喹啉与氯仿的摩尔比为1.0∶2.0~1.0∶2.4,反应22~26h,反应完成后,减压蒸馏除去乙醇和氯仿,再倒入蒸馏水,用稀盐酸中和至pH为7.0,抽滤得到棕色固体,真空干燥后得到棕色块状物体,研磨至粉末状后继续干燥,再用石油醚洗涤,洗涤液冷却,再过滤上清液以后剩下的固体用无水乙醇重结晶两次,干燥得到橙粉色细丝状晶体5-甲酰基-8-羟基喹啉;
(6)2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的制备:
在三颈烧瓶中加入摩尔比为1.0∶1.2~1.0∶1.8的5-甲酰基-8-羟基喹啉和氰基乙酸,再加入乙酸、乙腈,搅拌至溶解,溶解后加入哌啶,接着在90℃下反应34~38h,反应完成后,旋干溶剂并干燥,将固体研磨至粉末状后用三氯甲烷洗涤三次,再将固体干燥以后用乙醇重结晶两次,得到橘色粉末2-氰基-3-(8-羟基喹啉-5-基)丙烯酸;
(7)金属配合物BBT-Hg的制备:
取摩尔比为1.0:1.0~1.0:1.2的2,7-二溴-4,5-二丁氧基-[2,1-b:3,4-b']-二噻吩和2-氰基-3-(8-羟基喹啉-5-基)丙烯酸,依次加入单口瓶内,加热溶解,然后将HgCl2溶于无水甲醇中,并通过恒压漏斗缓慢滴加,并在75℃下反应22~26h,反应完成后冷却至室温,放入冰箱中过夜使固体完全析出,并在过滤后分别用水洗涤三次,无水乙醇洗涤三次,最终得到淡黄色固体含Hg配合物BBT-Hg;
(8)金属配合物BBT-Cd的制备:
配合物BBT-Cd的合成方法与配合物BBT-Hg的合成方法一致,将反应所需的HgCl2换成Cd(CH3COO)2·2H2O,合成后得到金黄色固体含镉配合物BBT-Cd;
(9)聚合金属配合物BDTT-BBT-Hg的制备:
取摩尔比为1.0:0.8~1.0:1.2的配合物单体BBT-Hg和2,6-二溴-4,8-二(5-(2-乙基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩BDTT加入单口烧瓶中,然后再加入锌粉、三苯基磷、双(三苯基膦)二氯化镍以及2,2’-联吡啶,再加入DMF,接着根据Yamamoto聚合反应,在氮气保护下,回流反应46~50h,反应结束后,冷却、过滤,用无水乙醇洗涤并干燥,得到深棕色固体产物BDTT-BBT-Hg;
(10)聚合金属配合物BDTT-BBT-Cd的合成;
聚合物BDTT-BBT-Cd的合成方法参照BDTT-BBT-Hg的合成,将反应需要的汞金属配合物BBT-Hg改为金属配合物BBT-Cd,合成后得到淡棕色固体粉末聚合配合物BDTT-BBT-Cd。
2.根据权利要求1所述的两种丁氧基苯并二噻吩衍生物合汞、镉共聚配合物BDTT-BBT-Hg、BDTT-BBT-Cd的用途,在染料敏化太阳能电池中用作染料敏化剂。
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