多重刺激响应的紫精类碘化亚铜簇及智能薄膜材料

The stimuli-responsive luminescent materials have attracted considerable attention owing to their potential application in data storage, environmental monitoring, drug delivery monitoring and light emitting device. Copper iodide clusters have the characteristics of strong luminance, high quantum yields and long lifetime, especially, their weak interactions usually vary with the exposure to multi-stimulus, resulting in the change of luminescent properties, so they are chosen as stimuli-responsive candidates. Viologen organic ligands as derivatives of 4,4'-bipyridine can reversibly receive and loss electrons, which serve as photoelectric stimuli-responsive molecules with wide applications in photochromic/electrochromic systems. This project aims at designing zero-dimensional multinuclear copper iodide clusters with easily distorted and flexible structures, induced by series of viologen ligands with strong optical activity, and pursing the intelligent multistimuli-responsive mechanism at two states with divergent electron disposition. The copper iodide cluster-based X-ray-switchable materials with high sensitivity to external stimulus are made into excellent smart membran materials, which are available for the X-ray detecting, the optical writing and reading of data as well as luminescent probes for labeling the nucleic acids in living cells.

刺激响应发光材料因其在信息存储、环境监测、药物缓释监测和发光器件等方面的潜在应用而备受关注。碘化亚铜簇具有量子产率高、发光强和寿命长等特点，特别是内部弱作用容易受外界刺激影响，进而引起发光性能改变，是一类良好的刺激响应性功能基团候选物。紫精是一类4,4'-联吡啶的衍生物，能够可逆地得失电子，是一类光电刺激响应性分子，在光/电致变色等方面有广泛应用。本项目拟设计合成一系列光活性紫精配体，进而诱导构筑结构灵活、易畸变的零维多核碘化亚铜簇，有利于实现可控多重刺激响应性发光，揭示在不同的电子配置下多重刺激响应性发光机理。将筛选出X-射线为发光开关的可控多重刺激响应紫精类碘化亚铜簇制备成智能薄膜材料，应用于X-射线探测、光学存储系统中数据的写入/读取及生物体内核酸的标记等科研领域。

刺激响应性材料在智能玻璃、光信息存储、光开关、传感、分离、催化和纳米技术等领域的潜在应用而备受关注。在这些刺激响应性材料中，大部分材料仅仅只会对一种外界刺激产生响应，而自然界中的刺激往往具有多重性，因而，多重刺激响应材料是智能响应材料领域的热点之一。由于紫精基材料在多种外界刺激下可发生电子转移，是一类能够多重刺激响应的优良候选者，然而这方面的研究还处于萌芽状态，没有形成系统的理论，亟待我们深入研究紫精基结构单元自组装方式、多重刺激响应性性能及其结构-性能微观机制。本项目已通过精准结构设计将缺电子的紫精衍生物配体与富电子组分复合到同一材料中，调控缺电子基团的接受电子能力，改变富电子部分的供电子能力，发挥电子供受体协同作用，创造多个合适的电子转移通道，实现多重刺激智能响应性，复合功能性有机分子制备出性能优良的智能薄膜材料。在此基础上，研究构筑单元自组装方式对π-π、氢键、卤素氢键等分子间弱相互作用的影响，进而探究分子间弱作用力在电子转移过程的关键角色，探讨其电子转移、电荷转移和能量转移等重要过程，重点探索其对光、热、电和气体小分子等外界刺激响应性机理，结合理论计算揭示了其结构-性能间关系，为合理设计预期功能的刺激响应性智能材料提供新方法。在本项目支持下，共发表SCI论文5篇（其中，SCI二区以上4篇，IF>4.0的4篇），组建了一支结构合理的刺激响应性智能材料科研团队。