“连续流动光化学”合成含螺吡喃类等光敏分子的多酸材料及表面组装行为研究

Continuous-flow photochemistry has recently emerged as an alternative strategy for inorganic synthesis, as this technology could provide reduced reaction times, improved mass- and heat-transfer characteristics, straightforward scalability and the cost-effective way to harvest the product. In this project, an innovative approach, namely flow reaction under light irradiation, will be employed to access new, and fundamentally important classes of photoresponsive polyoxometalates composites. It will then investigate their self-assembly behavior on surface by STM technique. Key components of the proposed four-year program will focus on: 1) developing continuous-flow photochemistry platform by integrating real-time analytics and consequently, controlling chemical reaction conditions in a precise, automated way; 2) achieving polyoxometalates composites which contain photosensitive molecules such as Spiropyrans, Spirooxazines and unveiling the key advantages inherent to this technology when comparing with traditional batch-type protocols; 3) constructing the supramolecular system which is constituted by POMs (guest molecules) and two-dimensional hydrogen-bonding systems (host molecules), and investigating their unique assembling process on surface by STM to understand the intrinsic relationship between crystalline characters and observed nanostructures. It is expected the outcomes of the project will spur the development of devices for applications ranging from sensing to switches and storage.

“连续流动光化学”作为一种新兴手段，具有缩短反应时间、高效传质/传热、快速优化并放大反应、提高产率等优势，而其在无机合成中的潜力还远未被开发。本项目利用“连续流动光化学”，合成含螺吡喃、螺嗯嗪类等光敏分子的光响应型多酸材料并研究其表面自组装行为：1) 完善并发展“连续流动光化学”方法，搭建高效、实用并整合在线检测手段的反应装置，进行精确、即时的反应控制；2) 运用该方法制备含螺吡喃类等光敏分子的多酸材料，系统比较该方法相对于传统溶液合成的优势；3) 以多酸材料为客体分子，氢键结合的二维体系为主体分子，运用扫描隧道显微镜观察超分子体系的表面组装行为，揭示材料晶态结构和表面纳米聚集行为的相关性。本项目有助于发展具有应用前景的光敏器件和信息存储材料。

本常规面上项目 “连续流动光化学”合成含螺吡喃类等光敏分子的多酸材料及表面组装行为研究，围绕“连续流动光化学”方法制备多酸材料这一主题开展实验研究。. 按照计划书的要求, 已取得以下阶段性成果：1) 发展"连续流动光化学"技术，运用自行搭建的连续流动光化学装置开展实验, 深入理解该方法相对于传统溶液合成、水热合成等实验手段的优势；2) 利用该装置高效合成若干配位聚合物以及具有一定附加值的药物中间体, 与常用的批式反应进行比较，总结实验规律并尝试推广"连续流动光化学"方法在合成化学领域的应用(暨不仅仅局限于无机合成领域); 3) 已得到若干含多酸结构单元的有机-无机杂化材料，在阐明其结构特征的基础上，探索该类材料在降解有机染料过程中的光催化活性; 4) 对“连续流动光化学”方法在近期内的实例进行了梳理，展望其发展趋势, 发表了相关综述。. 该项目成果迄今发表于中国化学快报、无机化学学报、Dalton Trans.等学术刊物上共11篇 (其中“中国化学快报”封底文章1篇、“无机化学学报”封面文章1篇、“Dalton Trans.”封底文章3篇)，均标注项目资助号 (21771088)。已获国家发明专利授权5件以及授权实用新型专利2件, 负责人参加1次国际学术会议及2次国内学术会议并做口头报告。. 该方法在化学研究领域中无疑将不断完善并应用到生产实践，同时在工程、材料、生物、纳米研究领域持续交叉融合，快速发展。