A Spontaneous Structural Transition of {U(24)Pp(12)} Clusters Triggered by Alkali Counterion Replacement in Dilute Solution

作者：Gao Yunyi; Dembowski Mateusz; Szymanowski Jennifer E S; Yin Wenbin; Chuang Steven S C; Burns Peter C^*; Liu Tianbo^*

来源：Chemistry - A European Journal, 2017, 23(33): 7915-7919.

DOI：10.1002/chem.201701972

• lactinides
• ion selectivity
• isomerism
• structural transition
• uranyl peroxide cluster

A transition between two isomeric clusters involving the change of the main skeleton structure of a well-defined, rigid molecular cluster [(UO2)(24)(O-2)(24)(P2O7)(12)](48) , {U(24)Pp(12)}, is achieved by simply introducing proper alkali cations into its dilute aqueous solution. While the unique structural transition can be triggered by introducing any of the Na+/K+/Rb+/Cs+ alkali ions, the two isomers, Li/Na-{U(24)Pp(12)} and Na/K-{U(24)Pp(12)}, as typical macroions, can accurately choose among different alkali counter-cations based on their hydrated sizes, and the ion selectivity process clearly showed endothermic features. The preferred K+ and Rb+ ions have suitable sizes to be incorporated into the proper windows on {U(24)Pp(12)} nanocapsules, as supported by the transition points in both ITC studies and IR measurements.

• 出版日期2017-6-12