Two-dimensional square-grid iron(ii) coordination polymers showing anion-dependent spin crossover behavior

Abstract

Two Fe(II)-based coordination polymers [Fe(tpmd)₂(NCS)₂]·5.5H₂O (1) and [Fe(tpmd)₂(NCSe)₂]·7H₂O (2) with the framework of square-grid type have been assembled from FeSO₄·7H₂O, N,N,N′,N′-tetrakis(pyridin-4-yl)methanediamine (tpmd), and KNCS/KNCSe in methanol and characterized. By utilizing two pyridine groups of a tpmd ligand, 1 and 2 are formed in two-dimensional layered structures through coordination of octahedral iron(II) ions with the tpmd to NCS⁻/NCSe⁻ ligands in which they have a supramolecular isomorphous conformation. 1 shows a paramagnetic behavior between 2 and 300 K, while 2 exhibits two-step spin crossover (ca. 145 and 50 K) in the temperature range due to the coordination of NCSe⁻ ligands. At 300 K 2 is fully high-spin state. However, at 100 K 2 becomes ca. 50% high spin and 50% low spin iron(II) ions, which is verified by magnetic moments. In the structural analysis of 2 at 100 K, two different layers are observed with different bond distances around iron(II) ions in which the layers are stacked alternately.