Tuning Fe-Se Tetrahedral Frameworks by a Combination of [Fe(en)₃]²⁺ Cations and Cl^- Anions

A one-dimensional (1D) chain compound $$ (en = ethylenediamine), featuring tetrahedral FeSe₂ chains separated by [Fe(en)₃]²⁺ cations and Cl^- anions, has been synthesized by a low temperature solvothermal method using simple starting materials. The degree of distortion in the Fe-Se backbone is similar to previously reported compounds with isolated 1D FeSe₂ chains. ⁵⁷Fe Mössbauer spectroscopy reveals the mixed-valent nature of [Fe(en)₃]₃(FeSe₂)₄Cl₂ with Fe³⁺ centers in the [FeSe₂]^- chains and Fe²⁺ centers in the [Fe(en)₃]²⁺ complexes. SQUID magnetometry indicates that $$ is paramagnetic with a reduced average effective magnetic moment, μ_eff = 9.51 μ_B per formula unit, and a negative Weiss constant, θ = -10.9(4) K, indicating antiferromagnetic (AFM) nearest neighbor interactions within the [FeSe₂]^- chains. Weak antiferromagnetic coupling between chains, combined with rather strong intrachain AFM coupling, leads to spin-glass behavior at low temperatures, as indicated by a frequency shift of the peak observed at 3 K in AC magnetic measurements. A combination of [Fe(en)₃]²⁺ and Cl^- ions is also capable of stabilizing mixed-valent 2D Fe-Se puckered layers in the crystal structure of [Fe(en)₃]₄(Fe₁₄Se₂₁)Cl₂, where Fe₁₄Se₂₁ layers have a unique topology with large open pores. Property measurements of [Fe(en)₃]₄(Fe₁₄Se₂₁)Cl₂ could not be performed due to the inability to either grow large crystals or synthesize this material in single-phase form.