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A Spontaneous Structural Transition of {U 24 Pp 12 } Clusters Triggered by Alkali Counterion Replacement in Dilute Solution
Author(s) -
Gao Yunyi,
Dembowski Mateusz,
Szymanowski Jennifer E. S.,
Yin Wenbin,
Chuang Steven S. C.,
Burns Peter C.,
Liu Tianbo
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701972
Subject(s) - alkali metal , counterion , chemistry , ion , materials science , inorganic chemistry , organic chemistry
A transition between two isomeric clusters involving the change of the main skeleton structure of a well‐defined, rigid molecular cluster [(UO 2 ) 24 (O 2 ) 24 (P 2 O 7 ) 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.