Various approximate models to describe the electronic properties of some families of clusters are reviewed. They correspond to specific elementary situations close to the Fermi level where one or few electrons are either removed from (or added to) a closed shell wavefunction. Simple hole-particule excitations are also considered. The models discussed involve diatomics-in-molecules schemes, use of pseudopotential framework extended to replace inert atoms, and finally combinations of both techniques for excited states. Applications to electronic structure of alkaline earth clusters, rare-gas systems or chromophores interacting with rare-gas systems are given also prospects for more complex molecular nanosystems or assemblies.