A Series of Mesoporous Rare-Earth Metal-Organic Frameworks Constructed from Organic Secondary Building Units

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.