A pi-extended, redox-active tetradentate tetrathiafulvalene-fused salphen [salphen = N,N'-phenylenebis(salicylideneimine)] compound (L) was prepared via a direct Schiff-base condensation of the corresponding diaminetetrathiafulvalene (TTF) precursor with salicylaldehyde. Its chelating coordination ability has been demonstrated by the formation of the corresponding transition metal complexes in the presence of M(OAc)(2) center dot nH(2)O (M = CO(II), Ni(II), Cu(II)) and FeCl3 center dot 6H(2)O, Three complexes have been characterized by single-crystal X-ray diffraction analysis showing that the TTF-salphen ligand coordinates to the metal ions in a planar mode through the nitrogen and oxygen atoms in a N2O2 cis-configuration. In the case of Fe(III), a dinuclear oxo-bridged Fe(III) complex is formed. These paramagnetic complexes are promising building blocks for the construction of dual functional materials due to their unique structural features (planarity and rigidity) as well as their inherent redox properties.