Towards Halogen Bonding MOFs: Networking With a Polyiodinated and Perfluorinated Terphenyl Ligand and Divalent Zinc.

While halogen bonding has been employed for the construction of organic frameworks, no metal-organic frameworks (MOFs) with additional halogen bonding functionality are known to date. Here, we present a suitable ligand for such systems, which combines a polyiodinated and -fluorinated terphenyl core with two carboxyl groups for metal coordination. Depending on the crystallization conditions, the ligand assembles with bivalent zinc cations into three distinct crystalline systems, either: (i) a metal-containing hydrogen-bonded organic framework; (ii) a MOF; or (iii) one-dimensional metal-organic chains with intermolecular halogen bonding and hydrogen bonding between adjacent chains. The 1D chains (iii) are obtained when using carbon disulfide as the crystallization medium, underscoring the potential of uncommon solvents in the design of structurally diverse crystalline materials formed from different supramolecular interactions. This study showcases the role of noncovalent interactions and halogen chemistry in directing crystal packing and highlights the challenges associated with the preparation of porous halogen bonding MOFs.