Abstract
Tiny azacryptand 1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane ( L) upon reaction with 48% hydrobromic acid (containing <0.05% chloride contamination) forms hexabromide salt ( 1). Single crystal X-ray crystallographic investigation of the hexaprotonated bromide ( 1) shows no guest encapsulation inside the tiny cage. This bromide salt 1 with an empty proton cage has been utilized as the receptor for encapsulation of chloride ( 2) and fluoride ( 3). Crystallographic results of mixed chloride/bromide ( 2) and fluoride/bromide ( 3) complexes of L are examined, which show monotopic recognition of chloride in the case of 2 and fluoride in the case of 3 inside the proton cage with five bromide and three water molecules outside the cavity. Single crystals obtained from an experiment on mixed anionic system (chloride and fluoride), 1 shows selective encapsulation of fluoride, which supports the formation of complex 3 and crystals obtained upon treatment of 2 with tetrabutyl ammonium fluoride also yields complex 3. In a separate reaction between L and 49% hydrobromic acid containing higher chloride contamination (<0.2%) forms chloride/bromide salt ( 2). 1H NMR studies of 1 with sodium chloride and fluoride support the encapsulation of the respective anions inside the proton cage.
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