The perfluorinated cages with all the exo polarized Cδ+-Fδ-bonds have been proposed to be efficient containers of excess electrons.To manipulate the localizations and conversions of excess electrons and spin states,we presented the theoretical investigations on the double-cage-like single molecular solvated dielectron systems,e2@C20F18(NH)2C20F18(e2@BB')at the B3LYP/6-31G(d)+ 4s4p theory level.It's found that the lone pair of excess electrons is confined inside one cage(left or right)to form two different singlet electromers(1L and 1R),while the two excess electrons are,respectively,trapped inside different cages to form triplet structure(3,ground state).Interestingly,the application of small external electric field of 21(-21)× 10-4 au results in single electron transfer of 3 → 1L(1R)and such transfer is also a spin state conversion of T → S.