Metallic salts formed from fullerenes became popular because of their superconducting properties with a relatively high transition temperature, and were initially regarded as conventional metals and superconductors. Recently, owing to improved synthetic methods and a renewed interest in the study of their physical properties, many of them were found to exhibit exotic metallic and superconducting phases. In this paper, we summarize earlier results on unconventional metallic fulleride phases as well as the newly discovered expanded fulleride superconductors. The proximity of the Mott transition, a typical solid-state effect, results in molecular crystals, where molecular spectroscopic methods prove very successful. We concentrate on infrared and optical spectroscopy which is very well suited to follow metallicity and phase transitions in this class of substances.