Metamagnetism and Single-Chain Magnetic Behavior in a Homospin One-Dimensional Iron(II) Coordination Polymer

Reaction of FeCl2 center dot 4?H2O with KNCSe and pyridine in ethanol leads to the formation of the discrete complex [Fe(NCSe)2(pyridine)4] (1) in which the FeII cations are coordinated by two N-terminal-bonded selenocyanato anions and four pyridine co-ligands. Thermal treatment of compound 1 enforces the removal of half of the co-ligands leading to the formation of a ligand-deficient (lacking on neutral co-ligands) intermediate of composition [Fe(NCSe)2(pyridine)2]n (2) to which we have found no access in the liquid phase. Compound 2 is obtained only as a microcrystalline powder, but it is isotypic to [Cd(NCSe)2(pyridine)2]n and therefore, its structure was determined by Rietveld refinement. In its crystal structure the metal cations are coordinated by two pyridine ligands and four selenocyanato anions and are linked into chains by mu-1,3 bridging anionic ligands. Magnetic measurements on compound 1 show only paramagnetic behavior, whereas for compound 2 an unexpected magnetic behavior is found, which to the best of our knowledge was never observed before for a iron(II) homospin compound. In this compound metamagnetism and single-chain magnetic behavior coexist. The metamagnetic transition between the antiferromagnetically ordered phase and a field-induced ferromagnetic phase of the high-spin iron(II) spin carriers is observed at a transition field HC of 1300 Oe and the single-chain magnetic behavior is characterized by a blocking temperature TB, estimated to be about 5 K.