General molecular engineering rules for the optimization of two-photon sensitive cages are presented and examples for nitrobenzyl, indole and nitrophenethyl platforms are highlighted. The efficiency of electron donor and acceptor groups in dipolar structures and the length of the conjugated system in the photolabile protecting group on two-photon uncaging efficiency will be discussed, as well as the emergence of symmetrical platform based on bis-electron donor or on quadrupolar architectures. We will then present our first results on the nano-structuration of donor-acceptor systems based on nitrophenetyl platform using diethyleneglycol or pentaerythritol cores.