Dynamics of Cation-Induced Conformational Changes in Nanometer-Sized Uranyl Peroxide Clusters

Conformational changes of the pyrophosphate (Pp)-functionalized uranyl peroxide nanocluster [(UO₂)₂₄(O₂)₂₄(P₂O₇)₁₂]^48- ({U₂₄Pp₁₂}), dissolved as a Li/Na salt, can be induced by the titration of alkali cations into solution. The most symmetric conformer of the molecule has idealized octahedral (O) molecular symmetry. One-dimensional ³¹P NMR experiments provide direct evidence that both K⁺ and Rb⁺ ions trigger an O-to-D₄ conformational change within {U₂₄Pp₁₂}. Variable-temperature ³¹P NMR experiments conducted on partially titrated {U₂₄Pp₁₂} systems show an effect on the rates; increased activation enthalpy and entropy for the D₄-to-O transition is observed in the presence of Rb⁺ compared to K⁺. Two-dimensional, exchange spectroscopy ³¹P NMR revealed that magnetization transfer links chemically unique Pp bridges that are present in the D₄ conformation and that this magnetization transfer occurs via a conformational rearrangement mechanism as the bridges interconvert between two symmetries. The interconversion is triggered by the departure and reentry of K (or Rb) cations out of and into the cavity of the cluster. This rearrangement allows Pp bridges to interconvert without the need to break bonds. Cs ions exhibit unique interactions with {U₂₄Pp₁₂} clusters and cause only minor changes in the solution ³¹P NMR signatures, suggesting that O symmetry is conserved. Single-crystal X-ray diffraction measurements reveal that the mixed Li/Na/Cs salt adopts D₂ molecular symmetry, implying that while solvated, this cluster is in equilibrium with a more symmetric form. These results highlight the unusually flexible nature of the actinide-based {U₂₄Pp₁₂} and its sensitivity to countercations in solution.