Unveiling the Dynamical Assembly of Magnetic Nanocrystal Zig‐Zag Chains via In Situ TEM Imaging in Liquid

The controlled assembly of colloidal magnetic nanocrystals is key to many applications such as nanoelectronics, storage memory devices, and nanomedicine. Here, the motion and ordering of ferrimagnetic nanocubes in water via liquid‐cell transmission electron microscopy is directly imaged in situ. Through the experimental analysis, combined with molecular dynamics simulations and theoretical considerations, it is shown that the presence of highly competitive interactions leads to the formation of stable monomers and dimers, acting as nuclei, followed by a dynamic growth of zig‐zag chain‐like assemblies. It is demonstrated that such arrays can be explained by first, a maximization of short‐range electrostatic interactions, which at a later stage become surpassed by magnetic forces acting through the easy magnetic axes of the nanocubes, causing their tilted orientation within the arrays. Moreover, in the confined volume of liquid in the experiments, interactions of the nanocube surfaces with the cell membranes, when irradiated at relatively low electron dose, slow down the kinetics of their self‐assembly, facilitating the identification of different stages in the process. The study provides crucial insights for the formation of unconventional linear arrays made of ferrimagnetic nanocubes that are essential for their further exploitation in, for example, magnetic hyperthermia, magneto‐transport devices, and nanotheranostic tools. A competition of electrostatic and magnetic interactions in the assembly of ferrimagnetic nanocubes is revealed through a joint analysis of the particles motion via in situ liquid TEM and Monte Carlo modelling. Electrostatic‐induced orientation of the nanocube magnetic axes over time leads to strong magnetic attraction between neighboring nanocubes, resulting in unusual zig‐zig linear arrays.