Starting from the first organic spin ladder reported, a dithiophene‐tetrathiafulvalene salt ((DT‐TTF)2[Au(mnt)2]) (mnt = maleonitriledithiolate), two different approaches to enlarge the family of organic spin‐ladder systems are described. The first approach consists of a molecular variation of the donor; to that purpose, the new TTF derivative ethylenethiothiophene‐tetrathiafulvalene (ETT‐TTF, 3), is synthesized and structurally characterized. From this donor a new ladder‐like structure compound, (ETT‐TTF)2[Au(mnt)2] (4), isostructural with (DT‐TTF)2[Au(mnt)2], is obtained. However, the magnetic properties of 4 do not follow the known spin‐ladder behavior owing to orientational disorder exhibited by the ETT‐TTF molecules in the crystal structure. In the second approach, the acceptor complex is changed, either in the nature of the ligand or in the metal. With the [Au(i‐mnt)2]– salt (i‐mnt = iso‐maleonitriledithiolate), the new ladder‐like compound (DT‐TTF)2[Au(i‐mnt)2] (5), isostructural with 4, is obtained, but only as a minority product. Two other compounds with a different anion generated in situ, bearing a Au(I) dimeric core, were also isolated; (DT‐TTF)9[Au2(i‐mnt)2]2 (6) as the most abundant phase and (DT‐TTF)2[Au2(i‐mnt)2] (7) as another minority phase. Salt 7 is characterized by X‐ray crystallography as a chiral compound, due to the torsion of the ligands around the central Au–Au bond. The magnetic properties of (DT‐TTF)2[Au(i‐mnt)2] (5) indicate that it follows a spin‐ladder behavior and the electron paramagnetic resonance (EPR) data is fitted to the Troyer and Barnes and Riera equations with the parameters Δ/kB = 71 K, J∥/kB = 86 K, and J⟂/kB = 142 K, indicating a J⟂/J∥ ratio of 1.65. The change of the gold complex [Au(mnt)2] for its copper analogue, [Cu(mnt)2] also leads to a ladder‐like structure, (DT‐TTF)2[Cu(mnt)2] (8), which is isostructural with the gold analogue and with salts 4 and 5. The fully ionic salt (DT‐TTF)[Cu(mnt)2] (9) is also obtained. The magnetic properties demonstrated that compound 8 is the third organic spin‐ladder system of this family, and the values found by a fitting to the ladder equations were Δ/kB = 123 K, J∥/kB = 121 K, and J⟂/kB = 218 K, corresponding to a J⟂/J∥ ratio of 1.75, similar to that of 5 and close to that of an ideal spin ladder.
