CN105601560B - 弱光频率上转换三线态敏化剂及其应用 - Google Patents
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Abstract
本发明公开了一种弱光频率上转换三线态敏化剂及其应用，其分子结构式含有中心金属元素M以及有机基团R；所述中心金属元素M为过渡金属元素；所述有机基团R为羧基、氨基或者羟基。本发明公开的敏化剂具有生物偶联基团，可以与生物分子发生偶联反应，从而可以应用于弱光频率上转换对生物分子的检测领域；带有的有机基团还可以与聚合物反应，从而连接敏化剂与聚合物，因此本发明还公开了上述弱光频率上转换三线态敏化剂在制备聚合物基固态弱光上转换材料中的应用。
Description
技术领域
本发明属于非线性光学材料领域，具体涉及一类带有偶联基团的三线态敏化剂，通过该偶联基团可以进一步拓展弱光频率上转换技术的应用领域。
背景技术
三线态-三线态湮灭上转换（TTA-UC）是个多量子过程，通常需要将敏化剂和发光剂混合在一起构成三线态湮灭上转换双组分体系，基于三线态敏化剂和三线态发光剂分子间相互作用而产生的，是一个低能量（波长长）光转换为高能量（波长短）光的过程。其过程就是：i）敏化剂首先吸收一个光子到达激发态后通过系间窜越（ISC）到达其三线态；ii）由敏化剂到发光剂之间发生三线态-三线态能量转移（TTT）；iii）两个处于三线态发光剂发生三线态-三线态湮灭（TTA）并发射上转换荧光。整个TTA 上转换过程就是：敏化剂光子在基态时，吸收能量，被激发来到单线激发态，其通过系间窜越，到达三线激发态，又通过三线态–三线态能量转移，把此时的能量传递给受体（发光剂）光子（敏化剂光子需要和发光剂的碰撞传递能量），使其到达三线激发态，当处于三线激发态的发光剂光子达到一定浓度时，两个处于三线激发态的发光剂光子通过三线态-三线态湮灭（相互碰撞），在一定的几率上，将产生一个处于单线激发态的发光剂光子，另一个则回到基态，此时处于单重激发态的发光剂光子发射出荧光而回到基态。
三重态-三重态湮灭(TTA)上转换具有所需激发光能量低（在峰值功率为< 0.1W×cm-2的光强即可激发）、上转换量子效率高、吸光能力强、激发发射波长可调等优点，在光电器件与光反应等领域具有重要的潜在应用价值, 近年来受到了广泛关注。在TTA上转换体系中，由于TTA上转换过程首先需要三线态敏化剂对外来的入射光进行吸收，然后通过复杂的光物理化学过程，实现接受剂分子的荧光发射（能量低于入射光，波长发生反斯托克斯位移现象）。因此三线态敏化剂的光物理性质对于整个TTA上转换体系的性能至关重要。
在现有的TTA上转换体系中，敏化剂多是化学惰性的，不具有进一步的反应活性位点，这大大限制了TTA上转换技术的进一步拓展应用。本发明旨在为TTA弱光频率上转换提供一类具有偶联基团的三线态敏化剂。
发明内容
本发明的目的是为三线态-三线态湮灭（TTA）上转换体系提供一类具有偶联基团的敏化剂分子，通过偶联反应，敏化剂可以与生物分子、聚合物材料等实现连接，从而为TTA上转换技术提供潜在的应用。
为达到上述发明目的，本发明采用的技术方案是：一种弱光频率上转换三线态敏化剂，其分子结构式含有中心金属元素M以及有机基团R；所述中心金属元素M为过渡金属元素；所述有机基团R为羧基、氨基或者羟基。
上述技术方案中，所述弱光频率上转换三线态敏化剂的分子结构式为：
或者
式中X^Y二齿配体、Xˊ^Yˊ二齿配体独立的选自C^N二齿配体、N^N二齿配体或者C^C二齿配体；A为卤素。有机基团R位于二齿配体上；卤素A可以为氯；M为铱或者钌。
上述技术方案中，所述X^Y二齿配体、Xˊ^Yˊ二齿配体独立的选自以下化学结构式中的一种：
。
优选的技术方案中，所述弱光频率上转换三线态敏化剂的分子结构式为以下结构式的一种：
。
本发明还公开了一种双组份弱光频率上转换体系，包括上述弱光频率上转换三线态敏化剂、发光剂；所述敏化剂与发光剂的摩尔比为1∶20～1000。本发明还公开的双组份弱光频率上转换三线态体系所用的介质可以是有机溶剂、离子液体、微乳液等；其中有机溶剂可以是甲苯、N,N-二甲基甲酰胺（DMF）、 氯仿、四氢呋喃（THF）、二甲基亚砜（DMSO）等。
优选的技术方案中，本发明发光剂的分子结构式为以下一种：
。
发光剂结构式中，取代基R1可以为氢或者苯基。
本发明公开的敏化剂具有生物偶联基团，可以与生物分子发生偶联反应，从而可以应用于弱光频率上转换对生物分子的检测领域；因此本发明还公开了上述弱光频率上转换三线态敏化剂在检测生物分子中的应用。
本发明公开的敏化剂带有的有机基团可以与聚合物反应，从而连接敏化剂与聚合物，因此本发明还公开了上述弱光频率上转换三线态敏化剂在制备聚合物基固态弱光上转换材料中的应用。
本发明还公开了上述弱光频率上转换三线态敏化剂的制备方法，通过金属M的卤化物与含有有机基团R的配体化合物进行加热反应；然后经纯化分离可以得到弱光频率上转换三线态敏化剂。
比如以化学式为MA的金属M的卤化物与带有R基团的X^Y二齿配体反应；然后与Xˊ^Yˊ二齿配体加热反应，最后经过纯化分离得到对应的弱光频率上转换三线态敏化剂，结构式如下：
。
以化学式为MA的金属M的卤化物与带有R基团的X^Y二齿配体加热反应，然后经过纯化分离得到对应的弱光频率上转换三线态敏化剂，结构式如下：
。
由于上述技术方案运用，本发明与现有技术相比具有下列优点:
1．本发明首次公开了一种带有可以与生物分子偶联的有机基团的敏化剂分子，其还有中心过渡金属原子；与发光剂可以组成双组份弱光频率上转换三线态体系，具有优异的弱光上转换效率。
2．本发明公开的敏化剂组成的弱光频率上转换复合体系可以通过敏化剂分子上的偶联基团与生物分子连接，在弱光频率上转换对生物分子的检测分析中具有潜在的应用；也可以通过敏化剂分子上的偶联基团与聚合物实现连接，在以聚合物基质的固态弱光上转换领域具有潜在的应用的价值。
附图说明
图1为实施例四的双组份弱光频率上转换体系上转换发光照片图；
图2为实施例四的双组份弱光频率上转换体系上转换发光光谱图；
图3为实施例五的双组份弱光频率上转换体系上转换发光光谱图；
图4为实施例六的双组份弱光频率上转换体系上转换发光光谱图；
图5为实施例六的双组份弱光频率上转换体系上转换发光光谱图；
图6为实施例七的双组份弱光频率上转换体系上转换发光光谱图。
具体实施方式
下面结合实施例、附图对本发明作进一步描述：
实施例一 弱光频率上转换三线态敏化剂的合成
将4-甲基-4ˊ-丁酸-2,2ˊ-联吡啶和三氯化钌加入到乙二醇乙醚溶剂中，加热回流反应12小时后，将溶剂除去，常规重结晶得到了三（4-甲基-4ˊ-丁酸-2,2ˊ-联吡啶）合钌配合物。
。
实施例二 弱光频率上转换三线态敏化剂的合成
将C^N配体先通过与三氯化铱反应制备得到相应的氯桥配合物，然后进一步与4-甲基-4ˊ-丁酸-2,2ˊ-联吡啶反应24小时后，通过纯化得到如下的三线态敏化剂。
。
实施例三 弱光频率上转换三线态敏化剂的合成
将C^N配体先通过与三氯化铱反应制备得到相应的氯桥配合物，然后进一步与4-甲基-4ˊ-丁酸-2,2ˊ-联吡啶反应24小时后，通过纯化得到如下的三线态敏化剂。
。
实施例四
敏化剂的分子结构式为：
发光剂的分子结构式为：
将敏化剂与发光剂分散在甲苯中，配制成不同敏化剂和发光剂摩尔比的双组份弱光频率上转换三线态体系。在弱光场下（波长为532 nm，激发光能量密度为可获得蓝色上转换荧光，见附图1；附图2为上述双组份弱光频率上转换三线态体系的上转换发光光谱，敏化剂与发光剂摩尔比为1:20、1:200、1:350、1:500、1:600条件下的上转换效率依次为6%、18%、22%、24%、27%。
实施例五
敏化剂的分子结构式为：
发光剂的分子结构式为：
将敏化剂与发光剂分散在DMF中，配制成不同敏化剂和发光剂摩尔比的双组份弱光频率上转换三线态体系。在弱光场下（波长为532 nm，激发光能量密度为可获得蓝色上转换荧光；附图3为上述双组份弱光频率上转换三线态体系的上转换发光光谱，随着发光剂浓度的逐渐增大，上转换效率可达19%。
实施例六
敏化剂的分子结构式为：
发光剂的分子结构式为：
将敏化剂与发光剂分散在离子液体中，配制成不同敏化剂和发光剂摩尔比的双组份弱光频率上转换三线态体系。在弱光场下（波长为532 nm，激发光能量密度为可获得蓝色上转换荧光；附图4为上述双组份弱光频率上转换三线态体系的上转换发光光谱，其效率可达32%。
取敏化剂和发光剂摩尔比为（1:350）的双组份弱光频率上转换三线态体系。附图5为上述双组份弱光频率上转换三线态体系的上转换发光强度与激光功率的关系图，在波长为532 nm，不同激光功率下可获得蓝色上转换荧光。
实施例七
敏化剂的分子结构式为：
发光剂的分子结构式为：
通过敏化剂的羧基与牛血清白蛋白（BSA）分子进行偶联，将带有蛋白分子的三线态敏化剂与发光剂结合构成上转换体系，附图6为该上转换体系的上转换发光光谱，其上转换效率可达27.2%。该结果说明通过偶联基团的作用，可以将上转换技术与生物分析检测结合起来，本发明的敏化剂在生物检测方面具有广泛的应用前景。
实施例八
通过偶联基团的作用，将三线态敏化剂作为支链连接到聚合物材料上边，进一步与发光剂进行充分混合，得到的复合材料经检测也具有上转换效应。具体为将聚乙烯醇与实施例一的敏化剂反应得到侧链带有敏化剂的聚合物；然将该聚合物与实施例五的发光剂按照摩尔比1∶300混合制备上转换体系，得到聚合物基固态弱光上转换体系，具有近25%的上转换效率，高于未偶联敏化剂的聚合物基固态弱光上转换体系的21%的上转换效率。该结果说明通过偶联基团的作用，同样可以将敏化剂以共价键的形式与聚合物材料连接，可以增强内部的能量转移效率，提升上转换的光强。
Claims (6)
1.一种弱光频率上转换三线态敏化剂，其特征在于，所述弱光频率上转换三线态敏化剂的分子结构式为以下结构式的一种：
。
2.一种双组份弱光频率上转换体系，包括弱光频率上转换三线态敏化剂、发光剂；所述敏化剂与发光剂的摩尔比为1∶20～1000；所述弱光频率上转换三线态敏化剂的分子结构式为以下结构式的一种：
。
3.根据权利要求2所述双组份弱光频率上转换体系，其特征在于，所述发光剂的分子结构式为以下一种：
、、。
4.一种弱光频率上转换三线态敏化剂在检测生物分子中的应用；所述弱光频率上转换三线态敏化剂的分子结构式为以下结构式的一种：
。
5.一种弱光频率上转换三线态敏化剂在制备聚合物基固态弱光上转换材料中的应用；所述弱光频率上转换三线态敏化剂的分子结构式为以下结构式的一种：
。
6.一种弱光频率上转换三线态敏化剂的制备方法：通过金属卤化物与含有有机基团R的配体化合物进行加热反应；然后经纯化分离可以得到弱光频率上转换三线态敏化剂；所述金属卤化物为三氯化钌或者三氯化铱；所述含有有机基团R的配体化合物为4-甲基-4ˊ-丁酸-2,2ˊ-联吡啶；所述弱光频率上转换三线态敏化剂的分子结构式为以下结构式的一种：
。
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