Snapshots of Ce ₇₀ Toroid Assembly from Solids and Solution

Abstract

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 [Ce^IV₇₀(OH)₃₆(O)₆₄(SO₄)₆₀(H₂O)₁₀]^4-, part of a larger emerging family of M^IV₇₀-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-crystal X-ray diffraction. Fragments show evidence for templated growth (Ce₅, [Ce₅(O)₃(SO₄)₁₂]^10-) and modular assembly from hexamer (Ce₆) building units (Ce₁₃, [Ce₁₃(OH)₆(O)₁₂(SO₄)₁₄(H₂O)₁₄]^6- and Ce₆₂, [Ce₆₂(OH)₃₀(O)₅₈(SO₄)₅₈]^14-). Ce₆₂, an almost complete ring, precipitates instantaneously in the presence of ammonium cations as two torqued arcs that interlock by hydrogen boding through NH₄⁺, a structural motif not observed before in inorganic systems. The room temperature rapid assemblies of both Ce₇₀ and Ce₆₂, respectively, by the addition of Li⁺ and NH₄⁺, along with ion-exchange and redox behavior, invite exploitation of this emerging material family in environmental and energy applications.