Abstract
Our conceived approach based on the directed assembly of functional metal–organic squares (MOSs), 4‐membered ring (4MR) building units, permitted the construction of two novel zeolite‐like supramolecular assemblies (ZSAs), namely [Co4(ImDC)4(En)4]⋅9 H2O⋅1.5 DMF (ZSA‐10) and [Co4(ImDC)4(En)4]⋅7 H2O (ZSA‐11) (H3ImDC=4,5‐imidazoledicarboxylic acid, En=ethylenediamine, DMF=N,N‐dimethylformamide). The elected MOSs encompass both trans‐ and cis‐coordinated nodes, offering complementary peripheral functional groups for their directed assembly into zeolite‐like topologies via supramolecular hydrogen bonding interactions. Distinctly, ZSA‐10 possesses the underling MER zeolite topology and is the only pure MER framework material (without any supporting templates) exhibiting permanent porosity up to now. ZSA‐11 has the underlying ABW topology together with one type of narrow channel.
A new type of MOS was successfully synthesized and employed for the construction of two new ZSA materials with MER and ABW underlying topologies. The introduction of this distinct MOS attests to the prospect of constructing new ZSA materials, and at the same time magnifies the plausible use of 4MR SBUs for the construction of ZMOFs.