The synthesis of a new tetratopic extended-TTF (exTTF; 9,10-di(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene) ligand, bearing four pyridyl coordinating functions on the dihydroanthracenyl platform rather than on the 1,3-dithiol rings (previously described regioisomer), was reported. The self-assembly behaviors of both electroactive regioisomers were compared. While a M₄L₂ container was obtained with the previous one when reacted with the square planar Pd(dppf)OTf₂ complex, the new ligand, when reacted under the same conditions, affords a M₆L₃ hexagonal structure that is composed of nine electro-active subunits that can be reversibly oxidized.