Department of Advanced Materials Science, Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, 277-8561, Chiba, Japan.
Department of Applied Chemistry, Graduate School of Engineering, The University of Tokyo, Bunkyo-ku, 113-8656, Tokyo, Japan.
Nat Commun. 2023 Jun 9;14(1):3241. doi: 10.1038/s41467-023-38835-5.
Mechanically interlocked architecture has inspired the fabrication of numerous molecular systems, such as rotaxanes, catenanes, molecular knots, and their polymeric analogues. However, to date, the studies in this field have only focused on the molecular-scale integrity and topology of its unique penetrating structure. Thus, the topological material design of such architectures has not been fully explored from the nano- to the macroscopic scale. Here, we propose a supramolecular interlocked system, MOFaxane, comprised of long chain molecules penetrating a microcrystal of metal-organic framework (MOF). In this study, we describe the synthesis of polypseudoMOFaxane that is one of the MOFaxane family. This has a polythreaded structure in which multiple polymer chains thread a single MOF microcrystal, forming a topological network in the bulk state. The topological crosslinking architecture is obtained by simply mixing polymers and MOFs, and displays characteristics distinct from those of conventional polyrotaxane materials, including suppression of unthreading reactions.
机械互锁结构启发了众多分子体系的构建，如轮烷、索烃、分子结及其聚合物类似物。然而，迄今为止，该领域的研究仅关注其独特贯穿结构的分子尺度完整性和拓扑结构。因此，这种结构的拓扑材料设计尚未从纳米到宏观尺度得到充分探索。在这里，我们提出了一种超分子互锁体系 MOFaxane，由长链分子贯穿金属-有机骨架 (MOF) 的微晶体组成。在本研究中，我们描述了聚伪 MOFaxane 的合成，它是 MOFaxane 家族的一员。它具有多线程结构，其中多个聚合物链穿过单个 MOF 微晶体，在块体状态下形成拓扑网络。通过简单地混合聚合物和 MOF 即可获得拓扑交联结构，并且显示出与传统聚轮烷材料不同的特性，包括抑制解旋反应。
