Hydride-Reduced Eu₂SrFe₂O₆: A T-to-T' Conversion Enabling Fe²⁺ in Square-Planar Coordination

Low-temperature reaction of A-site-ordered layered perovskite Eu₂SrFe₂O₇ (T structure) with CaH₂ induces a shift in the Eu₂O₂ slabs to form Eu₂SrFe₂O₆ with a T' structure (I4/mmm space group) in which only the Fe cation is reduced. Contrary to the previously reported T' structures with Jahn-Teller-active d⁹ cations (Cu²⁺ and Ni⁺), stabilization of Eu₂SrFe₂O₆ with the Fe²⁺ (d⁶) cation reflects the stability of the FeO₄ square-planar unit. The stability of T'-type Eu₂SrFe₂O₆ over a T-type polymorph is confirmed by density functional theory calculations, revealing the d occupancy for the T' structure. Eu₂SrFe₂O₆ has a bilayer magnetic framework with an Fe-O-Fe superexchange J_∥ and an Fe-Fe direct exchange J_⊥ (where J_∥ > J_⊥), which broadly explains the observed T_N of 390-404 K. Interestingly, the magnetic moments of Eu₂SrFe₂O₆ lie in the ab plane, in contrast to the structurally similar Sr₃Fe₂O₄Cl₂ having an out-of-plane spin alignment.