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Inorg Chem ; 60(19): 14904-14912, 2021 Oct 04.
Article in English | MEDLINE | ID: mdl-34516081

ABSTRACT

LaxSr2-xNiRuO6, LaxSr4-xNiRuO8, and LaxSr3-xNiRuO7 are, respectively, the n = ∞, 1, and 2 members of the (Lax/2Sr1-(x/2))nSr(Ni0.5Ru0.5)nO3n+1 compositional series. Reaction with CaH2, in the case of the LaxSr2-xNiRuO6 perovskite phases, or Zr oxygen getters in the case of the LaxSr4-xNiRuO8 and LaxSr3-xNiRuO7 Ruddlesden-Popper phases, yields the corresponding topochemically reduced (Lax/2Sr1-(x/2))nSr(Ni0.5Ru0.5)nO3n-1 compounds (LaxSr2-xNiRuO4, LaxSr4-xNiRuO6, and LaxSr3-xNiRuO5), which contain Ni and Ru cations in square-planar coordination sites. The x = 1 members of each series (LaSrNiRuO4, LaSr3NiRuO6, and LaSr2NiRuO5) exhibit insulating ferromagnetic behavior at low temperature, attributable to exchange couplings between the Ni1+ and Ru2+ centers they contain. Increasing the La3+ concentration (x > 1) leads to a reduction of some of the Ru2+ centers to Ru1+ centers and a suppression of the ferromagnetic state (lower Tc, reduced saturated ferromagnet moment). In contrast, increasing the Sr2+ concentration (x < 1) oxidizes some of the Ru2+ centers to Ru3+ centers and enhances the ferromagnetic coupling (increased Tc, increased saturated ferromagnet moment) for the n = ∞ and n = 2 samples but appears to have no influence on the magnetic ordering temperature of the n = 1 samples. The magnetic couplings and influence of doping are discussed on the basis of superexchange and direct exchange couplings between the square-planar Ni and Ru centers.

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