Molecular materials built from coordination complexes exhibit properties that can be explained through intermolecular electronic interactions driven by the ligand moieties. The nature of the ligand in the precursor molecules governs the connectivity of the magnetic phases and the possibility of producing them by using a gas-phase process. Metallocenium, metal bisdithiolate materials, and solvated and solvent-free [M(tcne)2] (tcne=tetracyanoethylene) magnets illustrate such features.