The metal-driven self-assembly methodology has afforded a large panel of molecular polygons (triangle, square,...) and polyhedrons (cubes, prisms, ...). Nevertheless, very few of them are electro-active and none presents an electron-rich cavity. The topic of this thesis concerns the synthesis and characterization of the first examples of metal-based self-assembled electron-rich molecular cages, as well as the study of their capacity to include various molecular substrates. These new self-assembled discrete structures incorporate redox-active walls based on the tetrathiafulvalene (TTF) moiety, a well-established unit known as a redox modulator for varied molecular / supramolecular architectures. On this ground, several synthetic routes to various new ligands incorporating this unit (or derivatives such as BPTTF or exTTF) and two or four coordinating moieties have been developed. Electronic properties (spectroscopy, cyclic voltammetry) as well as structural features (DFT calculation, X-ray diffraction) of these systems have been determined and allow to anticipate their self-assembly behavior. The metal-driven self-assembly methodology was applied to these ligands from various metal complexes. A molecular triangle was characterized and demonstrates an excellent ability to bind a complementary electrodeficient molecule (C60). In addition, tetratopic ligands allowed the access of the first examples of TTF-based cages (prisms, cubes,...), with electron-rich cavities. These architectures have been characterized through various spectroscopic methods (eg DOSY, FTICR, ...) and in some cases by single crystal X-ray diffraction. Finally, the capacity of this new type of cavities to include varied molecular guests is discussed.
