磷光软盐的分子设计、制备及其应用研究

Recently, materials showing smart response to external stimuli have attracted considerable research interest because of their potential in various optoelectronic applications. The photophysical properties of these materials can be regulated through external stimuli, such as pH, chemical species, electric field, light, temperature, and so on. Phosphorescent soft salt complexes represent an emerging platform for the development of novel stimuli-responsive materials because of their ease of molecular design and preparation and intriguing photophysical properties. However, the development of soft salt-based stimuli-responsive phosphorescent materials has not attracted widespread attention. In this project, a series of stimuli-responsive optoelectronic materials based on phosphorescent soft salt complexes and polymers will be designed and prepared. The excited state properties of these soft salts will be modulated by the external stimuli. The effects of these stimuli on the photophysical properties, electrochemical properties, crystal structures and theoretical calculation results of these soft salt complexes and polymers will be systematically investigated and their structure-property relationships will be established. By regulating the photophysical properties of these materials through external stimuli, this allows us to achieve ratiometric and lifetime imaging of various intracellular analytes in real time. In addition, by taking advantage of the feature of the external stimuli that can induce the change of the physical properties of these materials, the optical information recording device will be constructed. Furthermore, data encrypton and decrypton can be realized for security protection via advanced optical imaging or two-photon excitation techniques.

近年来，刺激响应型材料在光电应用方面的巨大前景受到了广泛关注，它们可以通过外界刺激（如pH值、化学分子、电场、光、温度等）来实现光物理性质的调控。磷光软盐配合物具有分子设计简单、制备容易以及光物理性质优异等特点，是发展新型刺激响应型光电材料的良好平台。然而，磷光软盐的刺激响应型材料还未引起广泛关注, 因此本项目拟通过合理的分子设计, 合成一系列基于软盐配合物/聚合物的刺激响应型光电材料，透过各种外界刺激调控它们的激发态性质；系统地研究材料的光物理性质、电化学性质、晶体结构以及结合理论计算探究外界刺激对材料性质的影响及它们之间的关系，进一步实现它们在细胞内对不同分析物进行实时比率与寿命成像的应用。此外，利用材料在外界刺激下能够改变自身的光物理性质的特性，将其应用到光学信息记录与存储器件中，使信息加密和解密过程可以通过先进的光学成像技术得以实现。

通过弱静电或范德华作用力相结合的磷光软盐材料具有结构和激发态性质易调控等优势。因此，开展磷光软盐材料的研究在基础研究和应用领域具有重要意义。在本项目中，本项目以“设计并合成一系列磷光软盐配合物材料”为核心，以“发展新型软盐类刺激响应型光电材料并实现其生物检测与光学信息存储应用”为目标，聚焦构效关系的研究，并取得了一系列重要成果。例如, 设计了基于铂(II)配合物磷光软盐并研究了其在电场诱导下的自组装行为及光物理性质变化规律；提出了设计铂(II)配合物磷光软盐作为明亮的近红外探针应用在体内成像应用的新思路；提出了激发波长依赖的磷光调控新策略，实现了具有刺激响应性新型铂(II)配合物磷光软盐用于时间分辨成像技术的高级防伪应用。通过本项目的实施，无论是从新型磷光软盐的构筑还是刺激响应性能的调控来说，都取得了重要的研究成果，具有重要意义。该项目按预期计划执行，经费使用合理。在该项目的支持下，培养博士研究生3名、硕士研究生1名，并取得了一系列研究成果。在国内外学术期刊发表学术论文25篇，出版专著1本。