CN113278035B - 一类电刺激响应型铱（ⅲ）配合物及其应用 - Google Patents
一类电刺激响应型铱（ⅲ）配合物及其应用 Download PDFInfo
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Abstract
本发明公开了一类电刺激响应型铱(Ⅲ)配合物及其应用，通过在配合物的C^N配体的苯环或吡啶环的不同位点上修饰乙基吡啶盐单元构建紫精配体，而N^N配体上引入吸电子的酰胺基团或给电子的甲基后构成；其主要利用紫精结构可逆的氧化还原特性，结合给电子或吸电子基团对配合物电子转移态的影响，在外界刺激下，改变铱(Ⅲ)配合物的电子转移态而改变配合物的光物理性质，可实现肉眼可见的光颜色的多彩变化，可应用于信息存储和加密领域；在紫精类结构单元的氮原子上引入乙基基团后，使得带有乙基紫精配体的铱(Ⅲ)配合物具有良好的氧化还原可逆性和化学稳定性，在电致变色器件、信息存储器件、储能器件中可以有着良好的应用前景。
Description
技术领域：
本发明属于有机光电材料技术领域，具体涉及一类基于紫精配体的电刺激响应型铱 (Ⅲ)配合物及其应用。
背景技术：
近年来，具有光、电等刺激性响应的发光材料在生物医学与成像、光电器件、传感器、信息防伪与加密保护等领域有着重要的应用。目前，光、电刺激响应性材料主要包括螺吡喃类、偶氮苯类、二芳基乙烯类和紫精类化合物。其中，紫精类化合物材料具备优良的氧化还原可逆性，独特的光物理、光化学性质和电化学性质，是一类应用广泛的光电转换、光致变色和电致变色材料。
紫精类化合物主要的工作机理是：接收外界刺激，如电场或者光刺激后，在富电子无机阴离子或有机配体的协助下，发生电子转移，完成两步还原反应，表现出三种不同的状态(中性的V0、单自由基V·+和双电荷V2+)，这三种状态具有不同电子分布形式，导致不同的电子吸收带，继而伴随着材料颜色的改变。在信息存储器件中，紫精类化合物由于其阳离子形式与自由基形式之间的转换，使可见光区域发生吸收变化，实现信息变化与记录。此外，紫精类化合物上的氮原子的取代基不同，会影响其还原电位，从而影响其光物理性质。现今对紫精类化合物的研究一般集中在纯有机小分子上，主要致力于改变材料颜色，以发光作为信号输出的研究较少。而光是可以以极高的灵敏度检测到的信号之一，如能实现光信号输出将拓宽该类材料的应用前景，但是，值得注意的一点是，将外界刺激处理成发光信号的分子还需考虑它们的发光量子效率。
过渡金属铱(Ⅲ)配合物具有发光量子产率高、发光寿命长、斯托克斯位移大、光稳定性高、发光颜色易于调控和具有很强的自旋-轨道耦合等优异的光物理性质，在有机光电领域得到了广泛的研究和应用。并且，磷光铱(Ⅲ)配合物分子具有丰富的激发态性质，包括配体和金属间能量传递(MLCT)态、配体内部的能量传递(ILCT)态、配体与配体之间的能量传递(LLCT)态等，可以通过对配体的修饰而引起一系列激发态的变化。将紫精单元引入到铱(Ⅲ)配合物中，可以在传统的基础上，结合紫精结构的可逆氧化还原性质，应用于光电转换、电致变色器件中。如中国专利CN 105237578 B 公开的具有多重刺激响应特性的磷光铱配合物及其应用，其利用离子型过渡金属配合物电子捕获能力强，良好的刺响应性，通过改变主配体结构以及辅助配体上烷基链的结构，可实现发光性质的可逆性调节，完成发光淬灭到开启的过程。但是此类材料无法实现从初始发光到另一种颜色发光的转变，这将限制此类材料在信息加密、光电转换、电致发光变色器件上的进一步拓展应用。
发明内容：
本发明的目的在于提供一类基于紫精配体的电刺激响应型铱(Ⅲ)配合物及其应用，微调配合物结构即可实现光颜色的多色变化，且该类材料具有可逆的氧化还原性和良好的循环稳定性，可为电致变色器件、信息存储器件、储能器件的进一步开放提供新思路和新方法。
本发明的技术解决方案为：一类电刺激响应型铱(Ⅲ)配合物，其是在铱(Ⅲ)配合物的C^N配体的苯环或吡啶环的不同位点上修饰乙基吡啶盐单元构建紫精配体，而 N^N配体上引入吸电子的酰胺基团或给电子的甲基后构成，该类配合物的结构通式如下：
其中，C^N配体为下列中任意一个修饰乙基吡啶盐的紫精配体：
进一步地，该类材料上的C^N配体具有可逆氧化还原性质，其与修饰吸电子基或给电子基的N^N配体相互作用，可调控配合物的波长，在电刺激作用下可使材料产生肉眼可见的多色变化。
进一步地，该类化合物在外加电压的作用下具备良好的可逆性和化学稳定性。
利用上述电刺激响应型铱(Ⅲ)配合物制备出电致变色器件后，其通过具有可逆氧化还原性质的C^N配体与修饰吸电子基酰胺基或给电子甲基的N^N配体相互作用，实现材料的多色改变，可用于信息存储。
本发明的有益效果为：
1.本申请公开的电刺激响应型铱(Ⅲ)配合物，是将过渡金属铱(Ⅲ)配合物的发光寿命长、斯托克斯位移大的优点与紫精单元可逆的氧化还原性质结合起来，构建的一类新型电刺激响应型材料；其主要利用紫精结构可逆的氧化还原特性，结合给电子或吸电子基团对配合物电子转移态的影响，在外界刺激(化学刺激或光电刺激)下，改变铱 (Ⅲ)配合物的电子转移态而改变配合物的光物理性质，可实现肉眼可见的光颜色的多彩变化，可应用于信息存储和加密领域；
2.本申请通过在紫精类结构单元的氮原子上引入乙基基团，使得带有乙基紫精配体的铱(Ⅲ)配合物具有良好的氧化还原可逆性和化学稳定性，在电致变色器件、信息存储器件、储能器件中可以有着良好的应用前景；
3.本申请利用过渡金属铱(Ⅲ)配合物对外界刺激的敏感性和高发光量子效率，将外界刺激(如光、电、化学物质等)反射成发光信号发出，便于灵敏检测，可作为高效的新型光电转换、电致变色器件。
附图说明：
图1为过渡金属铱(Ⅲ)配合物Ir-1在加入硼氢化钠前后在乙腈溶液中的发射光谱图；
图2为过渡金属铱(Ⅲ)配合物Ir-2在加入硼氢化钠前后在乙腈溶液中的发射光谱图；
图3为过渡金属铱(Ⅲ)配合物Ir-1和Ir-2在滴定硼氢化钠溶液前在乙腈溶液中的发射光谱图；
图4为过渡金属铱(Ⅲ)配合物Ir-1和Ir-2在滴定硼氢化钠溶液后在乙腈溶液中的发射光谱；
图5为以过渡金属铱(Ⅲ)配合物Ir-1制备的电致变色器件在紫外光激发下的图片；
图6为以过渡金属铱(Ⅲ)配合物Ir-1制备的电致变色器件加电测试之后在紫外光激发下的图片；
图7为以过渡金属铱(Ⅲ)配合物Ir-2制备的电致变色器件在紫外光激发下的图片；
图8为以过渡金属铱(Ⅲ)配合物Ir-2制备的电致变色器件加电测试之后在紫外光激发下的图片；
图9为过渡金属铱(Ⅲ)配合物Ir-1的循环伏安曲线图；
图10为过渡金属铱(Ⅲ)配合物Ir-1的恒流充放电曲线图(50次)；
图11为过渡金属铱(Ⅲ)配合物Ir-2的循环伏安曲线图；
图12为过渡金属铱(Ⅲ)配合物Ir-2的恒流充放电曲线图(50次)。
具体实施方式
为了更好地理解本发明专利的内容，下面通过具体的实施例和附图进一步说明本发明的技术方案，具体包括合成、材料结构表征和光响应过程测试。但这些实例并不限制本发明。在不背离本发明实质的情况下，对本发明方法、步骤或条件所作的修改和替换，均属于本发明的范围。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。
以下实施案例主要是在苯环与吡啶环对位引入对称的乙基吡啶盐构建紫精类C^N配体，C^N配体上引入吸电子基团酰胺基或给电子基团甲基，以配合物Ir-1和配合物Ir-2为例，其结构具体如下所示：
实施例一、配合物Ir-1的制备
具体合成路线如下：
(1)化合物1的制备：取2，5一二溴吡啶(4mmol，940mg)、对溴苯硼酸(4.1mmol，820mg)、碳酸钾(8mmol，1104mg)和四三苯基磷钯(0.2mmol，231mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次；分别注入20mL甲苯和乙醇的除氧溶液， 85℃下反应24h，冷却至室温，抽滤得溶液，减压蒸馏除去溶剂，再用饱和氯化钠溶液 (50mL)和二氯甲烷(100mL)萃取3次，分离有机相，浓缩溶剂并用柱层析分离得到化合物1；
(2)化合物2的制备：取化合物1(2.1mmol，491mg)和三水合三氯化铱(1mmol，352mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次；分别注入30mL乙二醇***和10mL水的除氧溶液，110℃下反应24小时后，冷却至室温，抽滤得到固体，依次用去离子水和乙醇清洗3遍，烘干后得到化合物2；
(3)化合物3的制备：取化合物2(0.29mmol，500mg)和自制bpy-dibu(0.59mmol，209mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次；分别注入20mL二氯甲烷和甲醇的除氧溶液，50℃下反应4小时，冷却至室温，减压蒸馏除去溶剂，柱层析分离法提纯得到化合物3；
(4)化合物4的制备：取化合物3(0.32mmol，500mg)、对吡啶硼酸(1.32mmol，163mg)、四三苯基膦钯(0.06mmol，69mg)和碳酸钾(1.28mmol，176mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次，分别注入15mL甲苯和乙醇的除氧溶液，85℃下反应24h，冷却至室温，抽滤得溶液，减压蒸馏除去溶剂，再用饱和氯化钠溶液(50mL)和二氯甲烷(100mL)萃取洗涤3次，分离有机相，减压蒸馏去溶剂，干法上柱，用柱层析分离法得到化合物4；
(5)配合物Ir-1的制备：取化合物4(0.17mmol，200mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次，注入1mL碘乙烷和10mL乙腈溶液，在40℃下反应24h，冷却至室温，减压蒸馏除去溶剂，加入饱和的六氟磷酸钾溶液中，常温下搅拌10h，抽滤得到固体配合物Ir-1。
实施例二、配合物Ir-2的制备
具体合成路线如下：
(1)化合物5的制备：取化合物2(0.29mmol，500mg)和4,4'-二甲基-2,2'-联吡啶(0.59mmol，109mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次；分别注入20mL二氯甲烷和甲醇的除氧溶液，55℃下反应5小时，冷却至室温，减压蒸馏除去溶剂，柱层析分离法提纯得到化合物5；
(2)化合物6的制备：取化合物5(0.29mmol，400mg)、对吡啶硼酸(1.20mmol，147mg)、四三苯基膦钯(0.05mmol，58mg)和碳酸钾(1.16mmol，160mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次，分别注入15mL甲苯和乙醇的除氧溶液，80℃下反应24h，冷却至室温，抽滤得溶液，减压蒸馏除去溶剂，再用饱和氯化钠溶液(50mL)和二氯甲烷(100mL)萃取洗涤3次，分离有机相，减压蒸馏去溶剂，干法上柱，用柱层析分离法得到化合物6；
(3)配合物Ir-2的制备：取化合物6(0.20mmol，200mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次，注入1mL碘乙烷和10mL乙腈溶液，在40℃下反应24h，冷却至室温，减压蒸馏除去溶剂，溶解在饱和的六氟磷酸钾的饱和溶液中，常温下搅拌12h，抽滤得到固体化合物Ir-2。
相关性能测试：
1.溶液状态下硼氢化钠滴定还原铱(Ⅲ)配合物实验
(1)配置10μM配合物Ir-1的乙腈溶液，移取2mL于荧光比色皿中，向比色皿中滴加硼氢化钠，测试不加硼氢化钠和滴加硼氢化钠的磷光发射光谱图。如图1所示，测试数据表明：滴加硼氢化钠后，最大发射峰由初始的607nm红移至635nm，发光强度没有明显的变化。
(2)配置10μM配合物Ir-2的乙腈溶液，移取2mL于荧光比色皿中，向比色皿中滴加硼氢化钠，测试不加硼氢化钠和滴加硼氢化钠的磷光发射光谱图。如图2所示，测试数据表明：滴加硼氢化钠后发射光谱有明显的蓝移，由初始的最大发射峰616nm蓝移至552nm。
由此可以看出，在溶液状态下，N^N配体上修饰了酰胺基和甲基后，初始状态时，Ir-1和Ir-2的波长相差不大，但在硼氢化钠溶液刺激之后，二者波长相差甚远，约83nm，这说明二者对波长调控的效果是不同的。Ir-1材料中由于修饰了吸电子基团酰胺基，在化学物质硼氢化钠的刺激下，波长发生明显的红移，而Ir-2材料中由于修饰了给电子基团甲基，在硼氢化钠的刺激下，波长发生明显的蓝移，这些变化都是可以通过肉眼可见的发光颜色变化所观测到的，由此可以看出，该类材料在复合不同基团的情况下，可实现从初始颜色发光到另一种颜色发光的改变，将发光特性不同的具体化合物作用到信息加密领域，并结合乙基紫精配体的氧化还原可逆性，将可构建一类新型依靠波长调控进行信息加密的刺激响应型材料。
2.过渡金属铱(Ⅲ)配合物Ir-1和Ir-2的电致变色器件的制备
将质量比为10:1:15的聚甲基丙烯酸甲酯PMMA(1g)、支持电解质高氯酸锂LiClO4(0.1g)、增塑剂碳酸丙烯酯PC(1.5g)溶于无水乙腈(5mL)，缓慢升温加热直至凝胶化。将铱(Ⅲ)配合物溶于无水乙腈溶液中(浓度：10-4M)，按质量比为3:2的凝胶电解质和配合物的乙腈溶液混合均匀，滴涂在ITO玻璃上，待溶剂自然挥发后，与另一片ITO玻璃重合，利用双面胶进行粘合，密封保护。
上述制备好的电致变色器件在紫外光下器件发光颜色状态如图5和图7所示，发现配合物Ir-1和Ir-2的发光颜色相似，为橙黄光。采用加电装置对器件两端施加2V电压，恒压10s，施加电压之后，器件在紫外光激发下发光颜色如图6和图8所示，以配合物 Ir-1为材料制作的器件发光颜色为橙红光，而以配合物Ir-2为材料制作的器件发光颜色为黄绿光。以上测试结果说明加电测试的结果与采用硼氢化钠还原的结果相符合。
3.铱(Ⅲ)配合物的循环伏安测试与恒流充放电测试
配合物Ir-1和Ir-2的电化学测试采用三电极体系进行测试。工作电极：铂碳电极；参比电极：Ag/AgNO3电极；对电极：铂柱电极；电解质：四丁基六氟磷酸铵的无水乙腈溶液(浓度为0.1M)；CV电位窗口：-2V～2V。1mg的配合物溶于3mL含电解质的无水乙腈中，将三电极置于无水乙腈中，注意保持互不接触且不触碰烧杯底部。用 Ar气除氧5min后，进行测试。
图9和图11分别为配合物Ir-1和配合物Ir-2的循环伏安曲线图，图10和图12分别是配合物Ir-1和配合物Ir-2的恒流充放电曲线图。由所得数据可知，在大约-1V的位置，出现一对可逆的氧化还原峰，可归属于紫精的氧化还原；并且在约-1.5V和+1.5V 处均有一对可逆的氧化还原峰。这些氧化还原峰是完全可逆的，在50个循环的氧化还原恒流充放电后，电位没有变化。以上说明配合物在外加电压下具有良好的可逆性和化学稳定性。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。
Claims (2)
1.一类电刺激响应型铱(Ⅲ)配合物在电致变色器件、信息存储和加密中的应用，其特征在于，通过具有可逆氧化还原性质的C^N配体与修饰吸电子基或给电子基的N^N配体相互作用，在电刺激作用下使材料产生肉眼可见的多色变化；
该配合物的结构式如下：
2.如权利要求1所述的一类电刺激响应型铱(Ⅲ)配合物在电致变色器件、信息存储和加密中的应用，其特征在于，该配合物在外加电压的作用下具备可逆性和化学稳定性。
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