Pillar-Layered Metal–Organic Frameworks Enabled by Pre-assembled Trianglsalen Macrocycles

The construction of metal-organic frameworks (MOFs) using pre-assembled building blocks enables the creation of more complex structures with enhanced functionalities. Here we employed trianglsalen macrocycles as building blocks to assemble pillar-layered MOFs. Coordination within the macrocyclic cavity distorts the macrocycle and generates unsaturated metal coordination sites, which in turn leads to diverse coordination orientations for the pillar ligands. By modulating the macrocyclic building blocks, metal salts and reaction conditions, we successfully obtained three distinct pillar-layered MOFs. The two MOFs exhibit 1D pillar-supported ladder structures, while another MOF features a bilayered 2D structure with regular triangular geometric defects, thus enriching the structural diversity and construction modes of MOFs.