CN114920701B - 基于三苯胺的电活性荧光离子液体、制备方法及在电致变色/电控荧光双功能器件中的应用 - Google Patents
基于三苯胺的电活性荧光离子液体、制备方法及在电致变色/电控荧光双功能器件中的应用 Download PDFInfo
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Abstract
一种基于三苯胺的电活性荧光离子液体、制备方法及其在电致变色/电控荧光双功能器件中的应用,属于电活性功能材料领域。本发明首先是使用TPAOME和BBr3发生脱甲基化反应制备TPAOH,然后在K2CO3条件下发生亲核取代反应,得到目标产物TPAOBr;再通过离子化反应制备EFIL‑TPA(Br),最后经过阴离子交换反应生成具有良好有机溶解性的以三苯胺基团为电活性基元和荧光发射基元、丁基咪唑基团为离子电荷中心的电活性荧光离子液体EFIL‑TPA,与苯醌对电极组装了电致变色/电控荧光的双功能显示器件。实验结果表明,本发明制备的双功能显示器件在降低功耗方面、提高离子传导率方面、荧光稳定性方面和荧光调控方面具有优势。
Description
技术领域
本发明属于电活性功能材料技术领域,具体涉及一种以三苯胺基团为电活性基元和荧光发射基元、丁基咪唑基团为离子电荷中心的基于三苯胺的电活性荧光离子液体、制备方法及其在电致变色/电控荧光双功能器件中的应用。
背景技术
电致变色/电控荧光双功能材料是在外界电压下发生可逆的颜色变化和荧光转换的智能显示材料。与传统的无机、小分子以及聚合物基的双功能的电活性材料相比,基于离子液体的新型双功能材料不仅可以实现容易的分子设计以及溶液加工特性,电活性荧光离子液体在调节材料的氧化还原性、提高热/电化学稳定性以及加快光学响应速度等方面也都展现出显著的优势。另外,离子液体有许多重要的固有特性,包括良好的电化学稳定性、热稳定性好、低挥发性、阻燃性和高的离子电导率。通常离子液体作为添加剂应用于锂电池的电解质,很小的添加剂量就能发挥很大的优势。然而,氧化还原型的电活性荧光离子液体目前在学术上的研究报道还较少,特别是在电致变色/电控荧光双功能显示领域。基于氧化还原型离子液体的这些优良特性有望显著提高电致变色/电控荧光双模可视化调制的响应速度、对比度、着色效率以及稳定性等性能。
本发明设计合成了一种基于三苯胺的氧化还原性电活性荧光离子液体(EFIL-TPA),构建了一个新型的小分子离子液体的电致变色/电控荧光双功能器件,这种分子设计展现了许多基于离子液体重要的特性,包括良好的电化学稳定性、热力学稳定性以及快速的光电响应速度,并详细研究了该离子液体的分子结构、对电极选择与电化学性能、电致变色性能和电控荧光性能间的构效关系,为高性能的电致变色/电控荧光双功能器件的设计合成及其组装提供了新的理论研究基础。
发明内容
本发明的目的是提供一种以三苯胺基团为电活性基元和荧光发射基元、丁基咪唑基团为离子电荷中心的基于三苯胺的电活性荧光离子液体、制备方法及其在电致变色/电控荧光双功能器件中的应用。
在本发明中,首先是使用TPAOME和BBr3发生脱甲基化反应制备TPAOH,然后在碱性K2CO3条件下发生亲核取代反应,得到目标产物TPAOBr;再通过离子化反应制备EFIL-TPA(Br),最后经过阴离子交换反应生成具有良好有机溶解性的电活性离子液体EFIL-TPA。在整个反应过程中,除了最后的阴离子交换反应,所有反应过程中都采用了薄层色谱法来监测反应程度。
本发明所述的基于三苯胺的电活性荧光离子液体(EFIL-TPA)的结构式和制备反应式如下:
本发明所述的基于三苯胺的电活性荧光离子液体的制备方法,其步骤如下:
(1)4,4'-二羟基三苯胺(TPAOH)的合成:将5~10mmol TPAOME溶解在30~60mL干燥的氯仿溶液中并冷却至-20~0℃,在搅拌下缓慢滴入25~50mL的BBr3和CH2Cl2的混合溶液(混合溶液中BBr3的量为0.02~0.04mol,CH2Cl2的量为0.39~0.78mol);在此温度下继续搅拌1~2h后,将反应混合物升温至室温继续反应15~24h;然后,在冰水浴条件下用甲醇终止反应,用旋转蒸发仪蒸干有机溶剂,并将残余物重新溶解在乙酸乙酯中,所得的溶液用饱和NaHCO3水溶液和蒸馏水依次洗涤,并加入无水MgSO4干燥,蒸干有机相溶液后得到棕色固体TPAOH;
(2)4-(4-溴丁氧基)-N-(4-(4-溴丁氧基)苯基)-N-苯基苯胺(TPAOBr)的合成:基于亲核取代反应制备单体TPAOBr,在室温条件下,将1,4-二溴丁烷的乙腈溶液逐滴加入到TPAOH和K2CO3的乙腈溶液中,1,4-二溴丁烷的用量为20~50mmol乙,TPAOH的用量为2~5mmol,K2CO3的用量为10~20mmol;然后升温至70~100℃下持续搅拌反应8~15h,去除有机相后通过柱层析色谱法进行纯化,采用石油醚和二氯甲烷的混合溶剂进行梯度洗脱,提纯得到灰白色固体TPAOBr;
(3)3,3'-(((苯基二酰基)双(4,1-亚苯基)双(氧))双(丁烷-4,1-二基))双(1-丁基-1H-咪唑)高氯酸盐(EFIL-TPA)的合成:EFIL-TPA(Br)是通过离子化反应合成制备,将1~2mmol TPAOBr和2~4mmol 1-丁基咪唑溶解在DMF(N,N二甲基甲酰胺)溶液中,并在N2保护下升温至130~170℃反应10~15h;再通过减压蒸馏除去DMF,收集得到棕色粘稠液体,即EFIL-TPA(Br);为了增加在有机溶液中的溶解性,进行了从溴离子到高氯酸盐的阴离子置换反应:将EFIL-TPA(Br)转移到10~20mL、0.5M的LiClO4水溶液中,在50~80℃下搅拌反应1~3h,观察到粘稠的沉淀物生成;将得到的粘稠的沉淀物溶解在二氯甲烷中,用二氯甲烷/饱和氯化钠溶液(体积比为1:1~3)进行萃取,将有机层减压蒸干低沸点的有机溶剂,从而得到本发明所述的基于三苯胺的电活性荧光离子液体EFIL-TPA。
本发明所述的基于三苯胺电活性荧光离子液体的双功能器件的组装方法,其步骤如下:
对电极(BQ/H2Q电极)的制备:称取3~5g PMMA、0.2~1g LiClO4、0.5~1g H2Q、0.5~1g BQ和5~15mL ACN,充分溶解后搅拌10~20h,在密封的容器中静置以去除气泡,得到均匀的粘稠状溶胶;使用四方涂布器在ITO导电玻璃的ITO导电面上刮涂一层上述制备的粘稠状溶胶,得到一层均匀的薄膜(30~80μm),并在50~80℃的真空干燥箱中干燥10~20h,得到对电极(BQ/H2Q电极);
双功能显示器件的组装:将空白的ITO(3×3cm2)导电玻璃(作为正极)和上述制备的BQ/H2Q(3×3cm2)对电极(作为负极)通过3M双面胶带制备成一个100~200μm间隙的三明治空心器件,用注射器将含有0.05M EFIL-TPA的乙腈溶液和0.1M LiClO4/PC的混合电解液注入组装好的三明治空心器件;为了确保密封性,器件缺口和所有的间隙都用紫外光固化剂进行密封;然后,将铜带粘贴在器件的正负两极,用来连接外接电源;这样就得到了基于三苯胺电活性荧光离子液体的电致变色/电控荧光双功能显示的器件。
附图说明
图1:本发明合成的电活性的荧光离子液体EFIL-TPA的核磁氢谱图;
图2:本发明合成的电活性的荧光离子液体EFIL-TPA的核磁碳谱图;
图3:本发明合成的电活性的荧光离子液体EFIL-TPA及其中间体的FTIR图;
图4:本发明合成的电活性的荧光离子液体EFIL-TPA及其中间体TPAOBr的TGA曲线比较图;
图5:本发明合成的电活性的荧光离子液体EFIL-TPA及其中间体TPAOBr和LiClO4/PC的混合电解液在三电极电池(玻碳电极为工作电极,Ag/Ag+电极为参比电极,Pt丝为对电极)体系中测试的CV扫描曲线图;
图6:本发明合成的电活性的荧光离子液体EFIL-TPA及其中间体TPAOBr与LiClO4/PC的混合电解液组装的双功能器件的CV扫描曲线图;
图7:本发明合成的电活性的荧光离子液体EFIL-TPA、TPAOBr分别与LiClO4/PC的混合电解液组装的双功能器件的交流阻抗谱图(EIS);
图8:本发明合成的电活性的荧光离子液体EFIL-TPA和LiClO4/PC的混合电解液组装的双功能器件在不同电压下的透过率变化图;
图9:本发明合成的电活性的荧光离子液体EFIL-TPA和LiClO4/PC的混合电解液组装的双功能器件在方波电压下透过率的循环曲线图;
图10:本发明合成的电活性的荧光离子液体EFIL-TPA和LiClO4/PC的混合电解液组装的双功能器件在不同电压下的荧光发射谱图;
图11:本发明合成的电活性的荧光离子液体EFIL-TPA和LiClO4/PC的混合电解液组装的双功能器件在方波电压下荧光发射的稳定性能图。
图1、2所示,所有核磁共振化学位移信号与相应分子的质子以及碳原子数量完全对应,初步证明了该电活性离子液体的成功合成。
图3中FTIR谱图可以得出,中间体TPAOH分子中3298cm-1附近的特征峰归因于与三苯胺相连的羟基的伸缩振动吸收,而1317cm-1的分子中C-N键的伸缩振动信号位于。此外,在TPAOBr中,酚羟基的特征宽频吸收带消失,同时出现了2920cm-1的烷基链上亚甲基信号峰。最后,在电活性离子液体EFIL-TPA的红外吸收曲线上,3424cm-1处的宽波吸收峰是咪唑阳离子的特征信号峰,同时1165cm-1处的吸收峰是C-N键伸缩振动信号,共同证明了该电活性离子液体分子(EFIL-TPA)的成功合成。
图4所示,基线与热失重曲线在最大斜率处的切线外推的交点温度定义为化合物的起始分解温度(Td),化合物质量损失5%时的温度为T5%。其中EFIL-TPA的Td为283℃,T5%为300℃。然而TPAOBr呈现出连续下降的TGA曲线,从100℃开始分子结构发生缓慢分解。这些结果证明了通过接枝离子液体基团,赋予了电活性离子液体EFIL-TPA更好的热力学稳定性。
图5所示,TPAOBr和EFIL-TPA的氧化还原中心都是电活性三苯胺中心,而起始氧化电位(Vonset)在一定程度上反应了电化学氧化的难易程度。其中,EFIL-TPA的Vonset(0.23Vvs.Ag/Ag+)小于TPAOBr的数值(0.40V vs.Ag/Ag+),同时EFIL-TPA的氧化峰值电位(0.48V)也低于TPAOBr(0.62V),这共同证明了在离子液体EFIL-TPA结构中,接枝离子液体基团后电化学活性显著提高。
图6中利用电活性离子液体EFIL-TPA和苯醌对电极(BQ/H2Q电极)组装了一个较低驱动电压的不对称的电致变色/电控荧光双功能器件。在此,测试了基于EFIL-TPA//BQ/H2Q组装的不对称双功能器件从0V到1.0V的循环伏安扫描曲线,显示出了一对三苯胺的氧化还原峰(0.98V/0.53V),扫描速度为50mV/s,起始氧化还原电位为0.6V,以期来降低该电致变色/电控荧光双功能器件的驱动电压。而组装的参比器件-TPAOBr//BQ/H2Q器件在0V到1.8V的CV扫描曲线中几乎没有显示出明显的氧化还原峰电流,且表现出较宽的电压驱动窗口,因而基于离子液体制备的EFIL-TPA//BQ/H2Q双功能器件在降低功耗方面更有优势。
图7选择浓度为0.05M TPAOBr或EFIL-TPA溶解在0.1M的LiClO4/PC溶液中构成一个混合电活性电解质体系,其离子电导率是通过交流阻抗法(EIS)分析得出的。通过对密封的阻塞电池(ITO/混合电解质/ITO)施加从高频1MHz到低频0.1Hz,扰动电压为5mV的信号进行交流阻抗测试。该阻塞电池的总电阻(Rs)是通过Nyquist图的中高频的直线延伸到阻抗的实部数据进行推断得出,通过以下公式计算出离子电导率。
σ=d/Rs×A.....................................................(1)
其中σ是离子电导率(S/cm),d是两个电极之间的电池间隙(cm),A是电极的活性面积(cm2),Rs是根据Nyquist图得到的电阻值;经过计算,含有EFIL-TPA的混合电解质体系的电导率为2.94×10-3S cm-1,而含有TPAOBr的混合电解质体系电导率为1.92×10-3S cm-1,这是由于接枝离子液体单元的分子提供了更多的载流子,一定程度上提高了离子导电率。总之,与含有TPAOBr的电解质相比,带有咪唑阳离子和高氯酸根阴离子的离子液体EFIL-TPA拥有更高的离子传导率。LiClO4/PC电解质体系电导率为2.15×10-3S cm-1。
图8是基于离子液体EFIL-TPA和苯醌对电极(BQ/H2Q电极)组装的器件显示出的透过率光谱变化曲线,最大的波谱响应在474nm处(ΔT1 62.0%)和740nm处(ΔT2 66.6%)。其中,图案化的器件外观颜色从无色(0V)变化到深褐色(1.0V),其颜色坐标分别为(0V,L*=14.81,a*=8.39,b*=0.56)和(1.0V,L*=15.40,a*=11.28,b*=1.23)。
图9为组装的器件在474nm处透过率光谱的变化曲线。最大透过率对比度可以稳定地波动循环500次,并且几乎没有观察到衰减,证明了该电致变色器件优异的稳定性。颜色转换时间被定义为达到90%的最大的透过率变化所需的时间。着色和漂白时间分别为0.58s和0.70s,这项指标优于大多数电致变色器件的性能,特别是基于离子液体的分子和一些电致变色小分子材料。
图10中研究了不同驱动电压下基于EFIL-TPA//BQ/H2Q器件的荧光调控行为。在无电压施加时,该器件发射明亮的蓝色荧光,发射中心波长为452nm,来自于中性态下三苯胺的局域态发射,其液态荧光量子产率为35%。当施加的电压从0V递增到1.0V,电压保持时间为20s,蓝色荧光发射强度下降直至淬灭,在1.0V时产生最大的荧光开关对比度为186。氧化态的阳离子自由基TPA+·引发了直接的本征荧光淬灭,这种机制的淬灭效率比较高效。当继续施加一个0V电压时,荧光发射也可以恢复到其初始状态。
图11为该电活性离子液体组装的电控荧光器件的稳定性测试。在经过500个周循环期后,荧光调制的开关对比度保持在最开始的96%,证明了该器件优异的电控荧光稳定性。此外,荧光强度90%转换的时间作为荧光开关响应速度,推算出荧光开关时间为1.8/0.57s。由于循环周期设定在较短的10s,荧光开关对比度下降到34.2。
具体实施方式
实施例1:本发明合成的电活性的荧光离子液体EFIL-TPA的合成制备
(1)4,4'-二羟基三苯胺(TPAOH)的合成:将化合物TPAOME(3.05g,10mmol)溶解在干燥的氯仿(60mL)溶液中并冷却至0℃,然后在搅拌下缓慢滴入BBr3和CH2Cl2的混合溶液,BBr3的量为0.04mol,CH2Cl2的量为0.78mol。在此温度下继续搅拌1h后,并将该反应混合物升温至室温继续反应18h。然后,在冰水浴条件下小心地用甲醇终止反应。用旋转蒸发仪蒸干有机溶剂,并将残余物重新溶解在乙酸乙酯(200mL)中。所得的溶液用饱和的NaHCO3水溶液(2×200mL)和蒸馏水(2×200mL)依次洗涤,并加入无水MgSO4干燥,蒸干有机相溶液后得到棕色固体TPAOH(2.05g)。
(2)4-(4-溴丁氧基)-N-(4-(4-溴丁氧基)苯基)-N-苯基苯胺(TPAOBr)的合成:基于亲核取代反应制备单体TPAOBr。在室温条件下,将1,4-二溴丁烷(50mmol)的乙腈溶液逐滴加到TPAOH(5mmol)和K2CO3(20mmol)的乙腈溶液中,升温至85℃下持续搅拌8h。去除有机相后通过柱层析色谱法进行纯化,流动相为石油醚(PE)和二氯甲烷(DCM)的混合溶剂进行梯度洗脱(PE和DCM的体积比为0.33~4:1),提纯得到灰白色固体TPAOBr(1.60g)。
(3)3,3'-(((苯基二酰基)双(4,1-亚苯基)双(氧))双(丁烷-4,1-二基))双(1-丁基-1H-咪唑)高氯酸盐(EFIL-TPA)的合成:IL-TPOI(Br)是通过离子化反应合成制备。将TPAOBr(2mmol)和1-丁基咪唑(4mmol)溶解在DMF溶液中,并在N2保护下升温至153℃反应12h。通过薄层色谱法进行分析,原料在反应进行5h后消失。再通过减压蒸馏除去DMF,收集到棕色粘稠液体EFIL-TPA(Br)。最后,为了增加在有机溶液中的溶解性,进行了从溴离子到高氯酸盐的阴离子置换反应。将EFIL-TPA(Br)转移到20mL、0.5M的LiClO4水溶液中,并加热到50℃下搅拌反应1h,在反应过程中观察到粘稠的沉淀物生成。随后,将粘稠的沉淀物溶解在二氯甲烷中,用二氯甲烷/饱和氯化钠溶液(体积比为1:1~3)进行萃取,将有机层减压蒸干低沸点的有机溶剂,从而得到本发明所述的基于三苯胺的电活性荧光离子液体EFIL-TPA(1.95g)。
实施例2:基于离子液体EFIL-TPA的双功能器件的组装
对电极(BQ/H2Q电极)的制备:按比例称取PMMA(3.1g)、LiClO4(0.5g)、H2Q(0.5g)、BQ(0.5g)和ACN(10mL),并充分溶解搅拌12h,在密封的小瓶中静置以去除气泡,得到均匀的粘稠状溶胶。使用四方涂布器在ITO导电面上刮涂一层上述制备的浆料,最终得到一层均匀的薄膜(50μm),并在50℃的真空干燥箱中干燥12h,得到对电极(BQ/H2Q电极);
随后,将空白的ITO(3×3cm2)导电玻璃和上述BQ/H2Q(3×3cm2)电极通过3M双面胶带制备成一个100μm间隙的三明治空心器件,用注射器将含有0.05MEFIL-TPA或0.05MTPAOBr的乙腈溶液和0.1M LiClO4/PC的混合电解液注入组装好的三明治空心器件。为了确保密封性,器件缺口和所有的间隙都用紫外光固化剂进行密封。然后,将铜带粘贴在器件的正负两极,用来连接外接电源;这样就得到了基于三苯胺电活性荧光离子液体的电致变色/电控荧光双功能显示器件。
Claims (5)
1.一种基于三苯胺的电活性荧光离子液体,其结构式如下所示:
2.权利要求1所述的一种基于三苯胺的电活性荧光离子液体的制备方法,其步骤如下:
(1)TPAOH的合成:将5~10mmol TPAOME溶解在30~60mL干燥的氯仿溶液中并冷却至-20~0℃,在搅拌下缓慢滴入25~50mL的BBr3和CH2Cl2的混合溶液,混合溶液中BBr3的量为0.02~0.04mol,CH2Cl2的量为0.39~0.78mol;在此温度下继续搅拌1~2h后,将反应混合物升温至室温继续反应15~24h;然后,在冰水浴条件下用甲醇终止反应,用旋转蒸发仪蒸干有机溶剂,并将残余物重新溶解在乙酸乙酯中,所得的溶液用饱和NaHCO3水溶液和蒸馏水依次洗涤,并加入无水MgSO4干燥,蒸干有机相溶液后得到棕色TPAOH固体,即4,4'-二羟基三苯胺;其中,TPAOME和TPAOH的结构式如下所示,
(2)TPAOBr的合成:基于亲核取代反应制备单体TPAOBr,在室温条件下,将1,4-二溴丁烷的乙腈溶液逐滴加入到TPAOH和K2CO3的乙腈溶液中,1,4-二溴丁烷的用量为20~50mmol,TPAOH的用量为2~5mmol,K2CO3的用量为10~20mmol;然后升温至70~100℃下持续搅拌反应8~15h,去除有机相后通过柱层析色谱法进行纯化,采用石油醚和二氯甲烷的混合溶剂进行梯度洗脱,提纯得到灰白色固体TPAOBr,即4-(4-溴丁氧基)-N-(4-(4-溴丁氧基)苯基)-N-苯基苯胺,其结构式如下所示,
(3)EFIL-TPA的合成:EFIL-TPA(Br)是通过离子化反应合成制备,将1~2mmol TPAOBr和2~4mmol 1-丁基咪唑溶解在DMF溶液中,并在N2保护下升温至130~170℃反应10~15h;再通过减压蒸馏除去DMF,收集得到棕色粘稠液体,即EFIL-TPA(Br);为了增加在有机溶液中的溶解性,进行了从溴离子到高氯酸盐的阴离子置换反应:将EFIL-TPA(Br)转移到10~20mL、0.5M的LiClO4水溶液中,在50~80℃下搅拌反应1~3h,观察到粘稠的沉淀物生成;将得到的粘稠的沉淀物溶解在二氯甲烷中,用体积比为1:1~3的二氯甲烷/饱和氯化钠溶液进行萃取,将有机层减压蒸干低沸点的有机溶剂,从而得到基于三苯胺的电活性荧光离子液体EFIL-TPA。
3.权利要求1所述的一种基于三苯胺电活性荧光离子液体在电致变色/电控荧光双功能器件中的应用。
4.如权利要求3所述的一种基于三苯胺电活性荧光离子液体在电致变色/电控荧光双功能器件中的应用,其特征在于:是将作为正极的ITO导电玻璃和作为负极BQ/H2Q对电极通过3M双面胶带制备成一个100~200μm间隙的三明治空心器件,用注射器将含有0.05MEFIL-TPA的乙腈溶液和0.1M LiClO4/PC的混合电解液注入组装好的三明治空心器件;然后,将铜带粘贴在器件的正负两极,用来连接外接电源;从而得到基于三苯胺电活性荧光离子液体的电致变色/电控荧光双功能显示的器件。
5.如权利要求4所述的一种基于三苯胺电活性荧光离子液体在电致变色/电控荧光双功能器件中的应用,其特征在于:是称取3~5g PMMA、0.2~1g LiClO4、0.5~1gH2Q、0.5~1g BQ和5~15mL ACN,充分溶解后搅拌10~20h,再在密封的容器中静置以去除气泡,得到均匀的粘稠状溶胶;然后在ITO导电玻璃的ITO导电面上刮涂一层粘稠状溶胶,得到一层均匀的30~80μm厚的薄膜,并在50~80℃的真空干燥箱中干燥10~20h,得到BQ/H2Q对电极。
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