Hierarchical Self-Assembly: Well-Defined Supramolecular Nanostructures and Metallohydrogels via Amphiphilic Discrete Organoplatinum(II) Metallacycles

Metallacyclic cores provide a scaffold upon which pendant functionalities can be organized to direct the formation of dimensionally controllable nanostructures. Because of the modularity of coordination-driven self-assembly, the properties of a given supramolecular core can be readily tuned, which has a significant effect on the resulting nanostructured material. Herein we report the efficient preparation of two amphiphilic rhomboids that can subsequently order into 0D micelles, ID nanofibers, or 2D nanoribbons. This structural diversity is enforced by three parameters: the nature of the hydrophilic moieties decorating the parent rhomboids, the concentration of precursors during self-assembly, and the reaction duration. These nanoscopic constructs further interact to generate metallohydrogels at high concentrations, driven by intermolecular hydrophobic and pi-pi interactions, demonstrating the utility of coordination-driven self-assembly as a first-order structural element for the hierarchical design of functional soft materials.