摘要/Abstract
网状框架具有结晶而延伸的多孔结构,不仅能将多种构筑模块按预期的方式有序组织形成介观材料,也因其可调控的精确结构成为研究基础科学问题的良好平台.机械互锁结构是利用分子间的机械作用将多种分子结合起来以协同实现复杂功能的分子集合体.将网状框架与机械互锁结构结合不仅能实现机械互锁结构的高维度有序组装以协同实现更复杂的分子机器的功能,也有望对更有应用前景的固相中机械互锁结构间的相互作用和微观机理有更深入的认识.本综述介绍了网状框架与机械互锁结构结合的研究领域的重要进展,第一部分在分别简要介绍网状框架和机械互锁结构的基础上阐述了两个领域结合的意义和策略;第二部分主要介绍了机械互锁结构作为构筑模块参与网状框架构建的系统性和代表性工作,包括含轮烷和索烃的构筑模块;第三部分则是介绍由机械互锁作用为主要相互作用构筑的网状框架,包括弹性编织框架和机械互锁框架,最后对全文进行总结并对该领域的后续发展方向予以探讨.
关键词: 金属有机框架, 共价有机框架, 机械互锁结构, 弹性编织框架, 机械互锁框架
The reticular frameworks have crystalline and extended porous structures, which can not only orderly organize a variety of building blocks to form mesoscopic materials in a programmable way, but also perform an excellent platform for basic scientific research because of the regulatable and precise structures. The representative systems of reticular frameworks are metal organic frameworks (MOFs) and covalent organic frameworks (COFs). Mechanically interlocked structures are molecular aggregations interacted through mechanical bond to realize complex functions. The combination of reticular frameworks and mechanically interlocked structures can promote the basic research of the microscopic interlocked behaviors in solid states; and also organize the interlocked structures in a regular way to achieve more complex functions. The mechanically interlocked structures can be introduced into reticular frameworks in two strategies, using mechanically interlocked structures as building blocks participating in the construction of reticular frameworks; and forming woven or interlocked frameworks with whole interlocked skeleton from unlocked precursors. This review summarizes the important progresses in the emerging research field combining the reticular frameworks and mechanically interlocked structures. In the first section, after the brief introduction of reticular frameworks and mechanically interlocked structures respectively, the significances and strategies of the combination of the above two fields is described. In the second section, we reveal the systematic and representative research of mechanically interlocked structure as a part of building blocks participating in the construction of reticular frameworks, including rotaxane, shuttle and catenate. The mechanical motions of rotaxanes and shuttle within MOFs are intensively studied. The representative methods and structures of introducing rotaxane or catenate into reticular frameworks are presented. In the third section, we exhibit the reticular frameworks constructed through mechanical bond as the main interaction within the whole skeleton from unlocked precursors, including resilient woven frameworks and mechanically interlocked frameworks. The typical woven or interlocked frameworks are mostly templated from special metal complexes and showing reversible transition between crystal and non-crystal maintaining the whole interlocked skeleton. Finally, we summarize the whole paper and discuss the future development in this crossing field, such as the applications of these combined systems should be expanded and the mechanically interlocked frameworks constructed through interlocking discrete molecular rings are expected due to the potential excellent elastic properties.
Key words: metal organic frameworks, covalent organic frameworks, mechanically interlocked structures, resilient woven frameworks, mechanically interlocked frameworks
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