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A series of diphenylimidazolyl calix[n]arenes (n = 4, 6, 8) obtained from readily available starting materials have been examined for selective extraction of monovalent (sodium, potassium, caesium and silver) and bivalent ions (barium and lead). It has been determined that the synthesized deep cavity imidazolyl calix[n]arenes can selectively recognize silver ions through interaction with the imidazolyl groups appended at their upper rim in contrast to their usually encountered complexation with the ester functionalities present at the lower rim. The silver extraction efficiency is limited in the absence of the calix[n]arene skeleton while it is radically influenced by the ring size of imidazolylcalix[n]arenes examined.
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