“…The chemistry of transition metals with dithiolene derivatives is a research field of high interest due to the outstanding physical properties that these compounds can show, as well as their wide structural diversity [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 ]. The dithiolenes are known as “non-innocent” ligands since they can form complexes with metals in different oxidation states giving rise to a rich redox chemistry of both the ligand and the metal center [ 16 ], leading to the formation of neutral, monoanionic and dianionic dithiolene derivatives [ 17 ]. We have previously studied the influence of several parameters, such as the nature of the dithiolene ligands, the size of the counter cations, the influence of crystallization conditions, as well as the type of iron precursor used, in the synthesis of a series of coordination polymers (CPs) containing the dianionic entities [Fe 2 (SC 6 H 2 X 2 S) 4 ] 2− (X = Cl or H) and [M 2 (µ-L) n ] 2+ (M = alkali metal) as counter-cations [ 18 , 19 ].…”