The synergy among twelve carboxylates from two hexavalent baskets 16- assisted the encapsulation of one divalent diammonium guest 32+-62+ and the formation of ternary [3-6⊂12]10-. The reduction of basket's multivalency, by photoinduced α-decarboxylation of 16- to give 23-, intercepted the interannular cooperativity operating in the stabilization of capsulpex [3-6⊂12]10- to dramatically diminish the binding affinity towards diammonium guests. As a result, the cationic guests were released into bulk water with 23- assembling into nanoparticles. With numerous drugs carrying positive sites, the finding reported here could now be examined for their light-promoted spatiotemporal delivery.