CN112094282B - 一种吲哚衍生物-edot类化合物及其制备与应用 - Google Patents

一种吲哚衍生物-edot类化合物及其制备与应用 Download PDF

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CN112094282B
CN112094282B CN202010766756.2A CN202010766756A CN112094282B CN 112094282 B CN112094282 B CN 112094282B CN 202010766756 A CN202010766756 A CN 202010766756A CN 112094282 B CN112094282 B CN 112094282B
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edot
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李维军
展望
张�诚
张凌
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Zhejiang University of Technology ZJUT
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Abstract

本发明提供了一种吲哚衍生物‑EDOT类化合物及其制备与应用，该化合物以吲哚衍生物为中心核，EDOT为外围基团，结构如式(1)所示。本发明的有意效果主要体现在：(1)本发明吲哚衍生物‑EDOT类化合物由于具有网状体型的空间结构，经电化学聚合成膜，所得到的薄膜表现出较大的比表面积，同时表现出良好的电致变色等电化学性能；(2)以本发明化合物为单体经电化学制得的薄膜能够实现从黄色至绿色(0.6V)与蓝色(0.9V)任意切换，光学对比度为20％～30％，响应时间为0.5～2s之间，在任意波段均表现出较为良好的光谱电化学稳定性，是一种低电压实现变色的电致变色材料。
Figure DDA0002614960650000011

Description

一种吲哚衍生物-EDOT类化合物及其制备与应用
(一)技术领域
本发明涉及一种吲哚衍生物-EDOT类化合物，及其制备方法与应用。
(二)背景技术
随着全球能源的急剧消耗和环境的不断恶化。节能环保材料吸引了人们的广泛关注。电致变色材料正是这样一种可以改变人类生产生活方式并且有助于合理利用能源的新型功能材料。该材料具有来源丰富、器件制备工艺简单及工作电压低等优点，且能广泛应用在智能窗、电子纸及显示器等领域。导电聚合物基电致变色材料因结构易修饰、着色效率较高、响应时间较短、光学对比度较高及较丰富的颜色变换而成为电致变色材料中最具有潜力的一类物质。
关于电致变色导电聚合物的变色电压大多数在1.0V以上，而关于低电压变色的电致变色导电高分子少有报道。
(三)发明内容
本发明目的是提供一种低电压变色的电致变色导电高分子化合物——吲哚衍生物-EDOT类化合物及其制备方法和应用，该化合物以吲哚衍生物为中心核、EDOT为外围基团，具有良好的电致变色性能。
本发明采用的技术方案是：
一种吲哚衍生物-EDOT类化合物，以吲哚衍生物为中心核，EDOT为外围基团，结构如式(1)所示：
Figure GDA0004080089710000021
本发明还涉及制备所述吲哚衍生物-EDOT类化合物的方法，所述方法包括：
(1)将EDOT溶解于无水四氢呋喃，在-78℃氮保下滴加正丁基锂溶液(浓度1～3mol/L)，保持该温度搅拌0.3～1h后加入三丁基氯化锡己烷溶液(浓度1～5g/mL)，三丁基氯化锡加入完成后恢复至室温搅拌6～24h，得到的反应液A经后分离纯化得到式2所示化合物；所述的EDOT、正丁基锂、三丁基氯化锡投料的物质的量之比为1:1～1.1:1～1.6；
Figure GDA0004080089710000022
(2)在氮气氛围下，将式1所示化合物、催化剂及式2所示化合物混合后溶于无水DMF中，升温到120±20℃，搅拌回流6～16h，得到的反应液B经分离纯化得到式(1)所示的吲哚衍生物-EDOT类化合物；所述式1所示化合物与催化剂、式2所示化合物投料的物质的量之比为1：0.001～0.01：4.0～6.0；所述的催化剂为四(三苯基膦)钯或醋酸钯。
优选的，步骤(1)中四氢呋喃用量为10～50mL/gEDOT。
优选的，步骤(2)中无水DMF用量为50～70mL/g式1化合物。
具体的，步骤(1)中分离纯化方法如下：将反应液A减压浓缩，以中性Al2O3为固定相、二氯甲烷为流动相进行洗脱，收集含目标产物的洗脱液，减压浓缩后得到式2所示的化合物。
具体的，步骤(2)中分离纯化方法如下：反应液B冷却至室温后倒入水中，过滤得到黄色固体，用二氯甲烷和水连续萃取，收集有机相，经无水硫酸钠干燥后减压浓缩，再用层析柱进一步纯化，以300～400目硅胶为固定相、体积比为1.5～5:1的石油醚/二氯甲烷的混合液为流动相进行洗脱，收集含目标化合物的洗脱液，减压浓缩得到式(1)所示的吲哚衍生物-EDOT类化合物。
本发明还涉及所述的吲哚衍生物-EDOT类化合物在制备低电压变色的电致变色材料中的应用。可以本发明吲哚衍生物-EDOT类化合物作为电致变色单体，采用电化学的方法成膜，该膜可作为电致变色材料用于智能窗、电子纸及显示器等领域。
电化学聚合成膜过程可如下：
将式(1)所示的基于吲哚衍生物的化合物溶解于二氯甲烷/乙腈体积比2：8的混合液中，加入四丁基高氯酸铵(TBAP)作为电解质，扫速为200mV/s，经0～1.2V循环伏安法电化学聚合成膜(pTTIEDOT薄膜)。
所述二氯甲烷的体积用量为1～2mL/mg式(1)化合物。
所述四丁基高氯酸铵的用量为0.1mol/L二氯甲烷。
本发明的有意效果主要体现在：(1)本发明吲哚衍生物-EDOT类化合物由于具有网状体型的空间结构，经电化学聚合成膜，所得到的薄膜表现出较大的比表面积，同时表现出良好的电致变色等电化学性能；(2)以本发明化合物为单体经电化学制得的薄膜能够实现从黄色至绿色(0.6V)与蓝色(0.9V)任意切换，光学对比度为20％～30％，响应时间为0.5～2s之间，在任意波段均表现出较为良好的光谱电化学稳定性，是一种低电压实现变色的电致变色材料。
(四)附图说明
图1为本发明实施例中pTTIEDOT薄膜的CV聚合曲线图；
图2为本发明实施例中pTTIEDOT薄膜在不同电压下的紫外吸收光谱图。
图3为本发明实施例中pTTIEDOT薄膜在674nm波段下的动力学稳定性。
图4为本发明实施例中pTTIEDOT薄膜在674nm波段下的光学对比度和响应时间。
(五)具体实施方式
为了加深对本发明的理解，下面将结合具体实施例对本发明做进一步详细描述，该实施例仅用于解释本发明，并不对本发明的保护范围构成限定。
实施例1：
步骤(1)化合物2三丁基(2-3，4-乙撑二氧噻吩基)锡的合成：
EDOT(15mmol，2.13g)溶解于100mL无水四氢呋喃，置于250mL单口圆底烧瓶中，抽真空充氮气循环三次。在-78℃氮气下慢慢滴加(1.6mol/L，15mmol，9.4mL)正丁基锂溶液，保持该温度搅拌0.5h后缓慢滴加三丁基氯化锡己烷溶液(1.2g/mL，20mmol，5.5mL)。在-78℃下搅拌0.5h后恢复至室温搅拌8h，反应结束后，反应液冷减压浓缩，以Al2O3填料层为固定相，二氯甲烷为流动相进行洗脱，得到含目标化合物的洗脱液，减压浓缩后得到式2所示的透明液体的化合物，产率90％。
Figure GDA0004080089710000051
步骤(2)化合物(1)TTIEDOT的合成：
将化合物1(1.07g，1.6mmol)(化合物1的合成参考文献：Angew.Chem.2020,132,1–6)置于100mL双口双底烧瓶中，快速加入催化剂Pd(pph3)4(18.5mg，0.016mmol)，抽真空充氮气循环三次。在氮保条件下依次加入步骤(1)所得的如式2所示的化合物(3.02g，7mmol)和30mL无水DMF，快速升温到120±20℃，搅拌回流14h。反应结束后，待反应液冷却至室温后，将反应液倒入水中，过滤得到黄色固体，用二氯甲烷和水连续萃取，收集有机相，经无水硫酸钠干燥后减压浓缩，再用层析柱进一步纯化，以300～400目硅胶为固定相，以体积比为3～5:1的石油醚/二氯甲烷的混合液为流动相进行洗脱，通过TLC确定部分含有目标化合物的洗脱液并收集含目标化合物的洗脱液，减压浓缩得到目标产物TTIEDOT，收率53％。1HNMR(500MHz，CDCl3)δ8.31(d，J＝8.5Hz，3H)，8.02(d，J＝1.5Hz，3H)，7.72(dd，J＝8.5，1.6Hz，3H)，6.37(s，3H)，5.04(q，J＝7.1Hz，6H)，4.46–4.32(m，12H)，1.68(t，J＝7.1Hz，9H).
实施例2：
将产物TTIEDOT(8.5mg，1mM)、TBAP(341mg，0.1M)为电解质，加入到容量瓶中，加入乙腈和二氯甲烷(体积比2:8)混合溶液10mL中，超声3min，充分溶解之后，用于电化学聚合。以ITO为工作电极、铂片(0.9*4cm)为对电极、Ag/AgCl为参比电极，采用循环伏安法0-1.2V成膜，在空白溶液中(0.1M TBAP溶解于乙腈)脱掺杂1min，制备得到的膜在烘箱中40℃干燥1小时后，在TBAP/乙腈中进行电化学、光学及电致变色性能测试。所有薄膜均是在含有TBAP的乙腈和二氯甲烷混合溶液中循环伏安10圈制备得到，测试条件为在含有TBAP的乙腈溶液中进行。
pTTIEDOT薄膜的CV聚合曲线图参见图1，pTTIEDOT薄膜在不同电压下的紫外吸收光谱图参见图2，pTTIEDOT薄膜在674nm波段下的动力学稳定性参见图3，pTTIEDOT薄膜在674nm波段下的光学对比度和响应时间参见图4。由图可见，该薄膜表现出良好的氧化还原性能，在0～0.9V电压阶跃，表现出黄色到绿色之间颜色的改变，674nm的光学对比度为25％，674nm下的着色和褪色时间分别为1.29s和0.59s，这些表明该材料是一种低电压实现变色的电致变色材料。与苯-EDOT类聚合物电致变色材料相比较，这类化合物经电化学聚合形成稳定的交联结构聚合物薄膜，电致变色稳定性得到了一定的改善。

Claims (7)

1.一种吲哚衍生物-EDOT类化合物，以吲哚衍生物为中心核，EDOT为外围基团，结构如式(1)所示：
Figure FDA0004080089700000011
2.制备权利要求1所述吲哚衍生物-EDOT类化合物的方法，所述方法包括：
(1)将EDOT溶解于无水四氢呋喃，在-78℃氮保下滴加正丁基锂溶液，
保持该温度搅拌0.3～1h后加入三丁基氯化锡己烷溶液，三丁基氯化锡加入完成后恢复至室温搅拌6～24h，得到的反应液A经后分离纯化得到式2所示化合物；所述的EDOT、正丁基锂、三丁基氯化锡投料的物质的量之比为1:1～1.1:1～1.6；
Figure FDA0004080089700000012
(2)在氮气氛围下，将式1所示化合物、催化剂及式2所示化合物混合后溶于无水DMF中，升温到120±20℃，搅拌回流6～16h，得到的反应液B经分离纯化得到式(1)所示的吲哚衍生物-EDOT类化合物；所述式1所示化合物与催化剂、式2所示化合物投料的物质的量之比为1：0.001～0.01：4.0～6.0；所述的催化剂为四(三苯基膦)钯或醋酸钯。
3.如权利要求2所述的方法，其特征在于步骤(1)中四氢呋喃用量为10～50mL/gEDOT。
4.如权利要求2所述的方法，其特征在于步骤(2)中无水DMF用量为50～70mL/g式1化合物。
5.如权利要求2所述的方法，其特征在于步骤(1)中分离纯化方法如下：将反应液A减压浓缩，以中性Al2O3为固定相、二氯甲烷为流动相进行洗脱，收集含目标产物的洗脱液，减压浓缩后得到式2所示的化合物。
6.如权利要求2所述的方法，其特征在于步骤(2)中分离纯化方法如下：反应液B冷却至室温后倒入水中，过滤得到黄色固体，用二氯甲烷和水连续萃取，收集有机相，经无水硫酸钠干燥后减压浓缩，再用层析柱进一步纯化，以300～400目硅胶为固定相、体积比为1.5～5:1的石油醚/二氯甲烷的混合液为流动相进行洗脱，收集含目标化合物的洗脱液，减压浓缩得到式(1)所示的吲哚衍生物-EDOT类化合物。
7.如权利要求1所述的吲哚衍生物-EDOT类化合物在制备低电压变色的电致变色材料中的应用。
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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003155288A (ja) * 2001-11-20 2003-05-27 Nec Corp 超分子構造を有するインドール系化合物およびそれを用いた二次電池並びにキャパシタ
CN101062929A (zh) * 2007-06-07 2007-10-31 复旦大学 基于三并咔唑的支化结构功能材料及其制备方法与应用
CN103374022A (zh) * 2013-07-02 2013-10-30 华南理工大学 低聚噻吩衍生物及其制备方法
CN103421012A (zh) * 2012-05-24 2013-12-04 南京工业大学 一种由芳基吲哚酮一步制备三并咔唑类材料的方法
CN103739607A (zh) * 2014-01-22 2014-04-23 无锡方圆环球显示技术股份有限公司 一种基于三并咔唑多臂结构红光材料及其制备方法与应用
CN104761573A (zh) * 2015-03-31 2015-07-08 浙江工业大学 一种三苯胺衍生物及其制备方法和应用
CN106188090A (zh) * 2016-07-05 2016-12-07 北京大学深圳研究生院 一种立体结构有机半导体材料及单体制备方法
CN106229413A (zh) * 2016-08-26 2016-12-14 中山大学 一种基于三并咔唑衍生物的空穴传输材料与聚合物协同作用的钙钛矿太阳电池及其制备方法
CN107163034A (zh) * 2017-06-01 2017-09-15 浙江工业大学 一种噻吩‑咔唑‑噻吩衍生物及其制备方法与应用
CN108794494A (zh) * 2018-06-18 2018-11-13 南京邮电大学 一种三并咔唑-芳香胺衍生物空穴传输材料及其制备方法与应用
CN108948026A (zh) * 2018-06-15 2018-12-07 南京邮电大学 一种三并咔唑-苯基空穴传输材料及其制备方法与应用
EP3489240A1 (en) * 2017-11-28 2019-05-29 Ecole Polytechnique Fédérale de Lausanne (EPFL) In-situ cross-linkable hole transporting triazatruxene monomers for optoelectronic devicestr
CN111269238A (zh) * 2018-12-05 2020-06-12 乐金显示有限公司 有机化合物、具有该化合物的发光二极管和发光装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007119386A (ja) * 2005-10-27 2007-05-17 Nec Tokin Corp インドール誘導体三量体の精製方法、該生成された三量体を含む電極活物質及び該電極活物質の製造方法並びにそれを用いた電気化学セル
JP5196928B2 (ja) * 2007-09-18 2013-05-15 キヤノン株式会社 有機発光素子及び表示装置

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003155288A (ja) * 2001-11-20 2003-05-27 Nec Corp 超分子構造を有するインドール系化合物およびそれを用いた二次電池並びにキャパシタ
CN101062929A (zh) * 2007-06-07 2007-10-31 复旦大学 基于三并咔唑的支化结构功能材料及其制备方法与应用
CN103421012A (zh) * 2012-05-24 2013-12-04 南京工业大学 一种由芳基吲哚酮一步制备三并咔唑类材料的方法
CN103374022A (zh) * 2013-07-02 2013-10-30 华南理工大学 低聚噻吩衍生物及其制备方法
CN103739607A (zh) * 2014-01-22 2014-04-23 无锡方圆环球显示技术股份有限公司 一种基于三并咔唑多臂结构红光材料及其制备方法与应用
CN104761573A (zh) * 2015-03-31 2015-07-08 浙江工业大学 一种三苯胺衍生物及其制备方法和应用
CN106188090A (zh) * 2016-07-05 2016-12-07 北京大学深圳研究生院 一种立体结构有机半导体材料及单体制备方法
CN106229413A (zh) * 2016-08-26 2016-12-14 中山大学 一种基于三并咔唑衍生物的空穴传输材料与聚合物协同作用的钙钛矿太阳电池及其制备方法
CN107163034A (zh) * 2017-06-01 2017-09-15 浙江工业大学 一种噻吩‑咔唑‑噻吩衍生物及其制备方法与应用
EP3489240A1 (en) * 2017-11-28 2019-05-29 Ecole Polytechnique Fédérale de Lausanne (EPFL) In-situ cross-linkable hole transporting triazatruxene monomers for optoelectronic devicestr
CN108948026A (zh) * 2018-06-15 2018-12-07 南京邮电大学 一种三并咔唑-苯基空穴传输材料及其制备方法与应用
CN108794494A (zh) * 2018-06-18 2018-11-13 南京邮电大学 一种三并咔唑-芳香胺衍生物空穴传输材料及其制备方法与应用
CN111269238A (zh) * 2018-12-05 2020-06-12 乐金显示有限公司 有机化合物、具有该化合物的发光二极管和发光装置

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Jin-Liang Wang等.p-Conjugated molecular heterojunctions with multi[60]fullerene: photophysical, electrochemical, and photovoltaic properties.《NewJ. Chem.》.2011,36第1583–1588页. *
Lin, Kaiwen等.Star-shaped trithiophene and hexathiophene functionalized truxenes: synthesis, electropolymerization, and electrochromism.《Reactive & Functional Polymers》.2020,104674. *
袁茂森. 三聚茚和三聚咔唑型多向电荷转移分子的合成及其光电性质.《中国博士学位论文全文数据库工程科技Ⅰ辑》.2009,B020-6. *

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