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An Imine‐Based Molecular Cage with Distinct Binding Sites for Small and Large Alkali Metal Cations
Author(s) -
Schouwey Clément,
Scopelliti Rosario,
Severin Kay
Publication year - 2013
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.201300098
Subject(s) - cage , alkali metal , chemistry , cooperativity , selectivity , imine , cage effect , metal , crystallography , inorganic chemistry , photochemistry , organic chemistry , biochemistry , mathematics , combinatorics , catalysis , photodissociation
The synthesis of a cylindrical, imine‐based cage composed of two trimeric metallamacrocycles is described. The cage acts as a heterotopic receptor for alkali metal cations. The small cations Li + , Na + , and K + bind to the outside of the cage with good selectivity for Li + , whereas the larger cations Rb + and Cs + are bound inside the cage to form unusual π complexes with a good selectivity for Cs + . Negative heterotopic cooperativity between the two binding sites is observed. The complexation of Cs + is associated with a color change, which enables the cage to be used as a specific sensor for Cs + .