Photo‐Induced Self‐assembly of Copolymer‐Capped Nanoparticles into Colloidal Molecules

Abstract Colloidal molecules (CMs) are precisely defined assemblies of nanoparticles (NPs) that mimic the structure of real molecules, but externally programming the precise self‐assembly of CMs is still challenging. In this work, we show that the photo‐induced self‐assembly of complementary copolymer‐capped binary NPs can be precisely controlled to form clustered AB x or linear ( AB ) y CMs at high yield ( x is the coordination number of NP‐ B s, and y is the repeating unit number of AB clusters). Under UV light irradiation, photolabile p ‐methoxyphenacyl groups of copolymers on NP‐ A *s are converted to carboxyl groups (NP‐ A ), which react with tertiary amines of copolymers on NP‐ B to trigger the directional NP bonding. The x value of AB x can be precisely controlled between 1 and 3 by varying the irradiation duration and hence the amount of carboxyl groups generated on NP‐ A s. Moreover, when NP‐ A * and NP‐ B are irradiated after mixing, the assembly process generates AB clusters or linear ( AB ) y structures with alternating sequence of the binary NPs. This assembly approach offers a simple yet non‐invasive way to externally regulate the formation of various CMs on demand without the need of redesigning the surface chemistry of NPs for use in drug delivery, diagnostics, optoelectronics, and plasmonic devices.