This is part of a general effort aimed at extending the range of molecular materials combining two properties in the same molecule and their tuning by changing the different electron ability of the metallocene and the radical units. The magnetic properties of different mono, bi and tri radicals have been studied.In addition, an interesting example of a photomagnetic system based on a supramolecular phenomenon in which a doublet species is converted into a singlet one is presented. Such ferrocene-polychlorotriphenylmethyl radicals present intramolecular electron transfer phenomenon which energy can be easily tuned by changing the substitutents of the donor or acceptor units or even the nature of the solvent. It is also described a novel valence tautomeric example combining an organic radical as acceptor unit and a ferrocene unit as the donor group. Finally, it has been proved that Ferrocene based polychlorotriphenylmethyl radicals systems also exhibits intense NLO responses that can be modulated at will simply tuning the donor and acceptor capabilities of the ferrocene and radical units.