Further development of metal–organic frameworks (MOFs) requires an establishment of hierarchical interaction within the framework. Herein, we report a series of mesoporous rare‐earth (RE) MOFs that are constructed from an unusual 12‐connected π‐stacked pyrene secondary building unit (SBU) and a typical 12‐connected RE₆ cluster (RE=Eu, Y, Yb, Tb, Ce). The judicious design of a butterfly‐shape pyrene ligand with a tert‐butyl substituent enables the formation of the disordered 12‐connected organic SBUs on its strong intermolecular π–π interactions. The assembly of 12‐connected inorganic cuboctahedron SBUs and 12‐connected organic distorted hexagonal prism SBUs generates an unprecedented network that can be further simplified into a 4,4‐connected pts net linked from planar square and tetrahedra. This work provides fresh insights into the design and synthesis of frameworks constructed from coordinatively, covalently, and noncovalently linked building units.

中文翻译：

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由有机二级建筑单元构建的一系列介孔稀土金属有机框架

金属有机框架（MOF）的进一步发展要求在框架内建立分层的交互作用。在此，我们报告了一系列中孔稀土（MO）MOF，这些MOF由不寻常的12个连接的π堆叠pyr二级建筑单元（SBU）和典型的12个连接的RE ₆簇（RE = Eu，Y， Yb，Tb，Ce）。带有叔丁基取代基的蝶形pyr配体的明智设计能够在其强烈的分子间π-π相互作用下形成无序的12连接有机SBU。12个连接的无机立方八面体SBU和12个连接的有机变形六边形棱镜SBU的组装产生了前所未有的网络，可以进一步简化为4,4个连接的pts网由平面正方形和四面体连接。这项工作为由协调，共价和非共价链接的建筑单元构建的框架的设计和合成提供了新的见解。