Heteroleptic Triple-Stranded Metallosupramolecules with Hydrophobic Inner Voids.

The systematic combination of well-defined coordination spheres and multiple types of ligands (heteroleptic) can lead to the generation of hierarchical metallosupramolecules with a high level of complexity and functionality. In particular, a specific multilevel coordination-driven assembly through the initiate generation of multinuclear clusters can form unique heteroleptic multiple-stranded supramolecular complexes. Herein, we report novel triple-stranded nickel-based supramolecules constructed from two different ditopic ligands ([1,1':3',1''-terphenyl]-4,4''-dicarboxylate (TP) and 2,6-pyridinedicarboxylate (PDA)) and a nickel precursor. The solid-state structures of the as-synthesized supramolecules revealed that three PDA ligands are employed to fabricate a tetranuclear ({Ni 4 }) cluster, and two {Ni 4 } clusters are assembled to form the final triple-stranded metallosupramolecules by three TP ligands. The bridging TP ligands also provide large inner voids with highly hydrophobic environments. Structural investigation of the generated complexes provided a deeper understanding of the aspects driving the formation of heteroleptic supramolecules, which is crucial for the design of multiple-strands with desired morphologies and functionalities.