Lin Yu-Shan, Lopez-Cabrelles Javier, Lin Chia-Her, Furukawa Shuhei
Institute for Integrated Cell-Material Science (WPI-iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.
Department of Chemistry, National Taiwan Normal University, Taipei, 11677, Taiwan.
Chem Asian J. 2025 Mar 17;20(6):e202401456. doi: 10.1002/asia.202401456. Epub 2025 Feb 6.
The architectural characteristics of metal-organic frameworks (MOFs) can be examined through their net topology, which consists of nodes and linkers. A node's connectivity and site symmetry are likely the key elements influencing the net topology of MOFs. Metal-organic polyhedra (MOPs) function effectively as nodes when used as supermolecular building blocks (SBBs). The SBB approach offers a powerful strategy for the deliberate design of macroscale materials, ranging from soft materials such as gels, polymers, and membranes to crystalline frameworks. However, achieving highly ordered structures with robust and air-stable rhodium-based MOPs (RhMOPs) presents a significant challenge. To investigate how to control the precise spatial distribution of RhMOPs as SBBs for constructing crystalline extended networks, here, we present a strategy for synthesizing MOFs by coordinating RhMOPs with rigid bridging linkers 1,4-diazabicyclo[2.2.2]octane (dabco). The resulting crystalline framework exhibited high microporosity and four times higher adsorption capacity than the parent MOP solids.
金属有机框架（MOFs）的结构特征可以通过其网络拓扑结构来研究，该结构由节点和连接体组成。节点的连接性和位点对称性可能是影响MOFs网络拓扑结构的关键因素。金属有机多面体（MOPs）用作超分子构建块（SBBs）时可有效地充当节点。SBB方法为从凝胶、聚合物和膜等软材料到晶体框架的宏观材料的精心设计提供了一种强大的策略。然而，用坚固且空气稳定的铑基MOPs（RhMOPs）实现高度有序的结构是一项重大挑战。为了研究如何控制作为SBBs的RhMOPs的精确空间分布以构建晶体扩展网络，在此，我们提出了一种通过将RhMOPs与刚性桥连连接体1,4 - 二氮杂双环[2.2.2]辛烷（dabco）配位来合成MOFs的策略。所得的晶体框架表现出高微孔率，吸附容量比母体MOP固体高四倍。
