engleski

Recent strategies for metal-organic cocrystal engineering — imine ligands with peripherally located carbonyl or morpholinyl fragment oxygen atoms as halogen bond acceptors

Halogen bonding is a versatile intermolecular interaction that has been utilized for the synthesis of a wide range of molecular and ionic materials. However, the use of halogen bonding for crystal engineering of new materials based on metal-organic subunits remains poorly explored and a challenge. Recently, our team has introduced a strategy that exploits carbonyl and morpholinyl oxygen atoms as halogen bond acceptors that can be readily introduced into the periphery of imine (Schiff base) ligands of coordinately unsaturated metal complexes. For example, using the carbonyl oxygen atom as the halogen bond acceptor enabled the synthesis of two isostructural metal-organic cocrystal families, based on copper(II) and nickel(II) centers.4 Of note is that the accompanying thermal analysis results validated the hypothesis that macroscopic properties of such materials can be readily tuned without changes to the overall crystal structures: four isostructural compounds were obtained as a combination of equivalent copper(II) and nickel(II) complexes with one stronger and one weaker halogen bond donor, with thermal stability of the metal- organic cocrystal being clearly determined by choice of halogen bond donor and the metal center. This presentation will provide an overview of these and other recent results in developing increasingly reliable strategies to design and synthesize metal-based halogen- bonded materials with controllable properties.

crystal engineering ; cocrystals ; coordination compounds ; halogen bonding

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