基于螺内酰肼水杨醛希夫碱金属配合物的新型光响应体系

Photoresponsive systems are attractive for the ability of reversibly change of their chemical and physical properties before and after light irradiation. Schiff bases of salicylaldehyde with amines (anils) have been long studied as simple photoresponsive systems with good performance. They are however suffered from a few drawbacks including poor thermostability and exhibition of only monotonous color after light exposure, which significantly limit their scope of practical application. In this proposal, spirolactam salicylaldehyde hydrazone metal complexes will be prepared by introducing metal ions and spironolactone dyes to anils. The complexes are expected to exhibit better thermostability and diverse colors upon light irradiation. Irradiating light with various wavelengths and intensity will be introduced to the complexes, and their photoresponsive properties will be carefully investigated by a variety of structural and spectroscopic measurements. The photoresponsive mechanism of the complexes, as well as the influences of different metal ions and the structures of complexes on the photoresponsive properties, will be studied. Optimization of the composition of complexes will result in new types of photoresponsive system with multiple colors, fast photoresponse, good reversibility, high fatigue resistance, excellent photobleaching resistance, and good thermostability of the light-exposed complex.

光响应体系是指能在光刺激下发生物理或化学性质可逆变化的体系。水杨醛希夫碱是一类结构简单、性能优良的小分子光响应体系。然而，由于水杨醛希夫碱光刺激产物稳定性差、显色种类单一，严重制约了其发展与应用。本项目拟以水杨醛希夫碱为基础，设计合成基于螺内酰肼水杨醛希夫碱金属配合物结构的新型光响应体系。通过引入金属离子，形成配合物，增强水杨醛希夫碱光刺激产物的稳定性；以不同的螺内酯染料结构作为显色基团，克服水杨醛希夫碱显色种类单一的缺点。选择多种波长、不同强度的光源对配合物体系进行光刺激，诱导其发生光响应。采用多种结构测试、光谱分析手段对体系的光响应性能进行表征，探索其光响应机理。研究不同金属离子、配合物结构对体系光响应性能的影响，总结调控规律。最终，以该调控规律为指导，优化配合物体系的组成，得到显色多样、响应迅速、可逆性好、抗疲劳性优良、抗光漂白能力强、光刺激产物稳定性高的新型光响应体系。

水杨醛希夫碱是一类结构简单、性能优良的小分子光响应体系。在本项目中，我们以螺内酰肼水杨醛希夫碱结构为基础，设计合成了一系列螺内酰肼水杨醛希夫碱金属配合物及衍生化合物，并开发了其多功能应用。首先，通过在螺内酰肼水杨醛希夫碱金属配合物体系中引入不同的荧烷母体结构，成功获得了一系列具有不同光响应性能的光致变色体系。尤其是通过对2-(2-氯苯胺基)-6-(二丁胺基)荧烷进行修饰，获得了在传统光致变色体系中十分少见的无色与黑色相互转换的光致变色体系。通过对这些体系光响应机理的系统研究，探讨了金属离子种类、螺内酰肼染料结构、溶剂环境等多种因素对于光致变色性能的影响。经过优化和筛选，得到了多种响应迅速、可逆性好、抗疲劳性优良、抗光漂白能力强、光刺激产物稳定性高、显色性能多样的新型配合物光响应体系。其次，利用所获得的新型光响应体系，结合其光响应机理，与不同的功能材料如激光染料、聚集诱导发光分子、高分子聚合物材料、金属有机框架材料等相结合，开发了其在光控三阶非线性开关、自加密型光信息存储材料、光致显色/荧光变化体系、光诱导自由基生成体系等方面的多种应用。