Hierarchically Responsive Alternating Nano‐Copolymers with Tailored Interparticle Bonds

Abstract Self‐assembly of inorganic nanoparticles (NPs) is an essential tool for constructing structured materials with a wide range of applications. However, achieving ordered assembly structures with externally programmable properties in binary NP systems remains challenging. In this work, we assemble binary inorganic NPs into hierarchically pH‐responsive alternating copolymer‐like nanostructures in an aqueous medium by engineering the interparticle electrostatic interactions. The polymer‐grafted NPs bearing opposite charges are viewed as nanoscale monomers (“nanomers”), and copolymerized into alternating nano‐copolymers (ANCPs) driven by the formation of interparticle “bonds” between nanomers. The resulting ANCPs exhibit reversibly responsive “bond” length (i.e., the distance between nanomers) in response to the variation of pH in a range of ~7–10, allowing precise control over the surface plasmon resonance of ANCPs. Moreover, specific interparticle “bonds” can break up at pH≥11, leading to the dis‐assembly of ANCPs into molecule‐like dimers and trimers. These dimeric and trimeric structures can reassemble to form ANCPs owing to the resuming of interparticle “bonds”, when the pH value of the solution changes from 11 to 7. The hierarchically responsive nanostructures may find applications in such as biosensing, optical waveguide, and electronic devices.