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Halogen-bond mediated assembly of metal-containing architectures

There is still a shortage of robust and transferable guidelines for deliberate supramolecular synthesis of metal-containing structures with precise and desirable metrics and topologies. Of the plethora of non-covalent interactions that can determine the assembly of a solid-state structure, the halogen bond is currently receiving considerable attention as a potentially important actor on the supramolecular stage. Similar yet different to its hydrogen bonding counterpart, the halogen bond is becoming a valuable tool in the crystal engineering toolbox. In fact, in many organic materials the halogen bond is used as the primary intermolecular interaction to dictate supramolecular self-assembly due to its strength, directionality and possibility for electrostatic fine-tuning of both the donor- and the acceptor moiety. On the other hand, relatively few metal-organic frameworks that rely on XBs have not received anywhere near the same attention. Therefore, we opted to employ a set of guidelines that has emerged from the engineering of organic solid-state systems and transfer them to the assembly of desirable metal-containing motifs. In this contribution we demonstrate how that principle can successfully be utilised in the rational design of a series of copper(II) and cadmium(II) coordination compounds. In addition, several structure-property correlations are presented (e.g. solubility, thermal stability, elasticity), and structural, thermal and spectroscopic data are complemented by CSD data mining. Extensive computational methods are used to facilitate the interpretation of the experimental efforts.

halogen bond; crystal engineering; coordination compounds

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