Inducing Ferrimagnetic Exchange in 1D-FeSe2 Chains Using Heteroleptic Amine Complexes: [Fe(en)(tren)][FeSe2]2.

ABSTRACT

[Fe(en)(tren)][FeSe2]2 (en = ethylenediamine, C2H8N2, tren = tris(2-aminoethyl)amine, C6H18N4) has been synthesized by a mixed-ligand solvothermal method. Its crystal structure contains heteroleptic [Fe(en)(tren)]2+ complexes with distorted octahedral coordination, incorporated between 1D-FeSe2 chains composed of edge-sharing FeSe4 tetrahedra. The twisted octahedral coordination environment of the Fe-amine complex leads to partial dimerization of Fe-Fe distances in the FeSe2 chains so that the FeSe4 polyhedra deviate strongly from the regular tetrahedral geometry. 57Fe Mössbauer spectroscopy reveals oxidation states of +3 for the Fechain atoms and +2 for the Fecomplex atoms. The close proximity of Fe atoms in the chains promotes ferromagnetic nearest neighbor interactions, as indicated by a positive Weiss constant, θ = +53.8(6) K, derived from the Curie-Weiss fitting. Magnetometry and heat capacity reveal two consecutive magnetic transitions below 10 K. DFT calculations suggest that the ordering observed at 4 K is due to antiferromagnetic intrachain interactions in the 1D-FeSe2 chains. The combination of two different ligands creates an asymmetric coordination environment that induces changes in the structure of the Fe-Se fragments. This synthetic strategy opens new ways to explore the effects of ligand field strength on the structure of both Fe-amine complexes and surrounding Fe-Se chains.