Self-Assembled Amphiphilic Janus Double Metallacycle

Abstract

A double metallacycle was prepared via the size-selective integrative self-sorting of four different building blocks driven by a reversible metal-ligand coordination interaction. A hydrophobic dendron was placed on a metallacycle and a hydrophilic dendron was attached to the other metallacycle, producing a two-faced Janus-type supramolecule with two distinct functionalities. In aqueous media, hierarchical self-assembly of the supramolecular system was induced by the combination of coordination interactions and hydrophobic-hydrophilic interactions resulting in the formation of micrometer-sized fiber-like structures, a morphology distinct from metallacycles bearing only one type of functionality. This study provides a versatile approach for the construction of Janus-type molecules and demonstrates that integrative self-sorting of a supramolecular coordination system can be utilized for the preparation of complex supramolecular systems with pre-designed functionalities and morphologies

Increasing structural and functional complexity in self-assembled coordination cages

“…In a similar fashion, Stang and coworkers prepared a heteroleptic double metallacycle by using integrative self-sorting as strategy. 154 They synthesized two ligands of different size, one with a hydrophobic side chain, the other one with a hydrophilic side chain. In addition, they prepared two pieces matching in size to each of the two dendrons and joined them with a bridge.…”

Oxidation triggers guest dissociation during reorganization of an FeII4L6twisted parallelogram

“…22 The phenomenon of mer or fac coordination is exclusive to octahedral coordination geometries around metal vertices. Other geometries, such as square planar motifs, lead to the formation of entirely different polyhedra, [23][24][25][26][27] while tetrahedral metal-binding pockets can lead to helicates or interlocked structures. [28][29][30][31][32][33][34] Other metal coordination motifs that are tied to their own rules of isomerism could lead to new families of metal-organic polyhedra.…”

Coordination‐Driven Terpyridine‐Based Twisted Prisms with Tunable Emissions and Hierarchical Self‐Assembly Properties

“…The hierarchical self‐assembly result of prism SA was possibly attributed to the following two aspects: i) the helical primitives from single supramolecule SA; ii) hydrophobic interactions from intermolecular alkyl chains. [ 27 ] The twisted prisms were stacked with a certain direction offset through the interaction between the hydrophobic chains to form a single helix. The helixes were further gathered to form a helicoid with a width of about 21 nm (Figure 5E).…”