Retrieving the Coassembly Pathway of Composite Cellulose Nanocrystal Photonic Films from their Angular Optical Response

Aqueous suspensions of cellulose nanocrystals (CNCs) are known to self‐assemble into a chiral nematic liquid crystalline phase, leading to solid‐state nanostructured colored films upon solvent evaporation, even in the presence of templating agents. The angular optical response of these structures, and therefore their visual appearance, are completely determined by the spatial arrangement of the CNCs when the drying suspension undergoes a transition from a flowing and liquid crystalline state to a kinetically arrested state. Here, it is demonstrated how the angular response of the final film allows for retrieval of key physical properties and the chemical composition of the suspension at the onset of the kinetic arrest, thus capturing a snapshot of the past. To illustrate this methodology, a dynamically evolving sol–gel coassembly process is investigated by adding various amounts of organosilica precursor, namely, 1,2‐bis(trimethoxysilyl)ethane. The influence of organosilica condensation on the kinetic arrest can be tracked and thus explains the angular response of the resulting films. The a posteriori and in situ approach is general; it can be applied to a variety of additives in CNC‐based films and it allows access to key rheological information of the suspension without using any dedicated rheological technique. The angular responses of photonic cellulose nanocrystal‐based films are investigated and related to the kinetic arrest transition occurring in the suspension upon solvent evaporation during the early stages of the film formation. How addition of sol–gel organosilica precursor to the suspension alters the resulting angular response, through a delayed kinetic arrest and a reduced vertical collapse of the structure, is elucidated.