Hierarchical packing of racemic metallosupramolecular cages with Ni(II)-based triple-stranded helicate building blocks

초록

Three novel hierarchical Ni-based metallosupramolecular cages were constructed from nickel ions, pyridine dicarboxylates and isophthalate derivative ligands (the substituents on C5 of isophthalate are methyl, tert-butyl and bromo groups). In every cage, two multinuclear nickel clusters, assembled from four nickel atoms and three pyridine dicarboxylate ligands, are interlinked by three isophthalate-derivative ligands to form a nickel-based triple-stranded helicate (TSH), which then becomes the supramolecular building block for the fabrication of a metallocage. Six homochiral TSH supramolecular building blocks, either left (M)-handed or right (P)-handed, are connected by four linking nickel atoms to generate M-6 and P-6 discrete racemic cage molecules (M-6 - cage with six M-TSHs; P-6 - cage with six P-TSHs). The crystal packing of the racemic cages was characterized by single-crystal X-ray diffraction. An additional cobalt-based molecular cage with 5-methylisophthalate bridging ligands was synthesized for host-guest interaction studies. The methyl groups in Co- and Ni-TSH can act as guest units to be accommodated in the cone-shaped metal clusters (host) of an adjacent cage.

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