Growth Mediated Disassembly of Cucurbit[8]uril Cross‐linked Static Cubic Self‐assembly of Silver Nanoparticles

Abstract

AbstractStatic self‐assembly resides in thermodynamically stable global minima of the energy landscape, whereas dynamic self‐assembly occupies local minima of the energy profile and remains in the ordered state for a limited time via dissipation of energy to surroundings. This makes the spatiotemporal control over the assembly and disassembly mechanism easily controllable in the case of dynamic self‐assembly. However, due to the higher thermal stability of static self‐assembly, it is very challenging to perform reverse engineering on these types of systems. Herein we report growth reaction‐based reversal of static silver cubes obtained via cucurbit[8]uril (CB[8]) crosslinked self‐assembly of silver nanoparticles (AgNP). The AgNP building units with variable CB[8] surface coverage have been used as seeds onto which deposition of gold via growth reaction has been performed. The disassembly of supracube structure has been controlled by the formation of [AuCl4]−–CB[8] complex and successive reduction of [AuCl4]− to Au0 on the surface of the seed. The resulting monodispersed isotropic nanoparticles, formed from the CB[8] based cubic self‐assembly after growth, exhibit Au−Ag bimetallic nature. Quenching of the fluorogenic response from the hydrophobic dye coumarin‐7, added after growth, suggests direct interaction with the metallic nanoparticle surface after disassembly and thereby confirms successful growth reaction mediated reversal of self‐assembly.