光响应型多孔分子笼

The preparation of new functional porous materials is an important goal in Materials Chemistry, with potential applications in gas storage, molecular separations, catalysis, and sensing. Photochromic molecules (such as diarylethene (DAE) derivatives) have demonstrated great potential to be molecular components of stimuli-responsive materials. Despite recent achievements in photo-responsive Metal Organic Frameworks (MOFs) and Covalent Organic Frameworks (COFs), precise control of the pore functions by light with photochromic building blocks remains to be a significant challenge..Here, I will develop a new stimuli-responsive supramolecular system to show controllably reversible photochemical reactions upon ultraviolet and visible light irradiation by introducing photochromic DAE units into Porous Organic Cages (POCs) – a new type of porous materials. This project aims to combine computational and experimental approaches to explore new DAE-cage materials with controllable photo-switching properties, and dynamic light-induced capture and release of guest molecules. To date, the field of photo-responsive POCs remains underexplored..This proposal is centered on the design, synthesis, characterization, and rationalization of DAE-cage materials for alkene/alkane separations. Various DAE building blocks will be prepared to assemble DAE-cages to achieve a reversible photo-switching property between the open- and closed- DAE form, and a stepwise photo-switching process via intermediates containing both the open‐ and the closed‐form building blocks, coexisting in a single cage assembly. In addition, I will develop a scrambled DAE-cage with different DAE building blocks in a single cage system which can achieve a controllable photo-switching process using various wavelengths of UV light to trigger photo-responsive behaviours..I will carry out a detailed study to determine light‐triggered structural changes in these DAE-cages using single-crystal X-ray diffraction and powder X-ray diffraction, and investigate the light ‐switchable guest uptake and release in these materials especially for alkene/alkane separations. This study would open a new direction of photo-responsive cages as platforms for various photo-chemical conversions and photo-modulation of porous properties. This project will represent a significant step forward in designing new smart materials for new energy applications.

设计合成新型光响应型功能材料是本世纪化学领域的重要研究热点之一，体现了人类对新能源的积极探索。申请人创新性提出将二芳基乙烯光响应基团引入多孔有机笼体系，利用分子笼的特定孔道结构释放光异构化活性，从而构建新型的光控多孔分子笼材料。本项目拟利用计算机模拟预测和设计分子笼拓扑结构，实现对分子笼精确可控合成，并对二芳基乙烯单元在分子笼中的光异构化行为进行了系统性探索；通过精准组装分子笼堆积结构以及精确调控微纳空间，实现光驱动承载在多孔分子笼材料上在炔烃/烯烃、烯烃/烷烃等气体分离方面的功能应用。.本项目的实施将为光响应型多孔分子笼材料的可控合成提供新的方法，为理解光控对多孔分子笼材料结构和性能的内在关系提供依据，对相似物理性质混合气体的高效分离技术，以及光控气体储存与释放的发展具有重要的意义。同时也为今后开发新型智能多孔材料在催化、传感、药物传输/缓释等领域打开了思路。

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