A study across scales to unveil microstructural regimes in the multivalent metal driven self-assembly of cellulose nanocrystals

complexation. Near-atomistic coarse-grained molecular dynamics simulations were developed to gain microscopic insight into the behaviour of this colloidal system. We found that the formation of different self-assembled architectures is driven by metal-nanocellulose complexation combined with the attenuation of electrostatic repulsion and water structuration around cellulose, leading to different microstructural regimes, from isolated nanorods to disconnected rod fractal clusters and rod fractal gels. These findings lay the foundation to unlock the full potential of cellulose nanocrystals as sustainable building blocks to develop self-assembled materials with defined structural control for a range of advanced applications.