A number of sodium salt complexes of p-tert-butylcalix[4]arene tetraethyl ester, 1, were isolated both with and without upper-rim encapsulated solvent. Selective decomplexation of lower rim bound sodium cations and upper rim encapsulated solvent molecules could be successfully achieved using low pressure light sources. Oxidation of the counter anion at the lower rim of p-tert-butylcalix[4]arene tetraethyl ester triggered both the upper and lower rim decomplexation process. The extent of decomplexation at both rims is controlled both by the nature of the counter-anionic species at the lower rim and by the fate of the photoproducts generated. The calixarene host molecule, 1, remains intact during the decomplexation process
