Ferromagnetism in [Mn(Cp*) 2 ] + ‐Derived Complexes: the “Miraculous” Stacking in [Mn(Cp*) 2 ][Ni(dmit) 2 ]

The synthesis and characterisation (X-ray structure and magnetism) of metal complexes (Ni, Au) with the [Mn(Cp*)2]+ cation and the dmit2− and dmid2− ligands are reported. [Mn(Cp*)2][Ni(dmit)2] (1) and [Mn(Cp*)2][Au(dmit)2] (2) exhibit the same structural arrangement, built on stacks of [Ni(dmit)2]− pairs separated by two [Mn(Cp*)2]+ cations, showing a ···D+D+A−A−D+D+A−A−··· motif. On the contrary, the dmid2− derivative [Mn(Cp*)2][Ni(dmid)2]·CH3CN (3) exhibits a totally different structure, built on mixed layers composed of one [Ni(dmid)2]− unit separated by two [Mn(Cp*)2]+ cations, showing a ···D+D+A−D+D+A−···motif. The layers are separated from each other by perpendicular [Ni(dmid)2]− unit…