Molecular building blocks (MBBs) have been utilized previously as components in the design and synthesis of novel metal-organic frameworks (MOFs), most based on the assembly of metal-carboxylate clusters and polytopic organic ligands of various shapes. Here we introduce the use of the MBB approach in the rational assembly of pre-designed polytopic organic linkers and hetero-coordinated single metal, MNxOy -type, clusters into new zeolite-like metal-organic frameworks (ZMOFs) with extra-large cavities. Three novel porous anionic ZMOFs, rho-ZMOF, sod-ZMOF and usf-ZMOF, have been constructed by metal-ligand directed assembly of rigid and directional tetrahedral building units, InN4 synthesized in-situ, and doubly deprotonated bis(bidentate) imidazoledicarboxylic acid ligands (HImDC) in the presence of different structure directing agents (SDAs). The design strategy, synthesis, structure, porosity, and their inclusion and sensing chemistry will be discussed.

Y. Liu, V. Kravtsov, R. Larsen, M. Eddaoudi, Chem. Commun. (2006) 1488.