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Crystallization at the solid-liquid interface is difficult to spectroscopically observe and therefore challenging to understand and ultimately control at the molecular level. The Ce70-torroid formulated [CeIV70(OH)36(O)64(SO4)60(H2O)10]4-, part of a larger emerging family of MIV70-materials (M = Zr, U, Ce), presents such an opportunity. We elucidated assembly mechanisms by the X-ray scattering (small-angle scattering and total scattering) of solutions and solids as well as crystallizing and identifying fragments of Ce70 by single-crysta