Solid solution studies of layered honeycomb-ordered phases O₃–Na₃M₂SbO₆ (M=Cu, Mg, Ni, Zn)
Complete solid solutions with the composition Na₃M 2–x M´ x SbO₆ where M, M´=Cu, Mg, Ni, Zn have been synthesized by conventional solid state techniques and were investigated using X-ray diffraction, magnetic susceptibility and optical measurements. All compositions crystallize in a monoclinic unit cell and exhibit a layered structure with a honeycomb cationic ordering within the slabs. These compounds also exhibit Curie–Weiss behavior at high temperature and the magnetic moment values verify the presence of Cu²⁺ and/or Ni²⁺. The antiferromagnetic order of Na₃Ni₂SbO₆ is suppressed upon substitution of Ni²⁺ with Mg²⁺ or Zn²⁺. The spin gap observed in Na₃Cu₂SbO₆ is also suppressed by substitution of Cu²⁺ with Mg²⁺ or Zn²⁺. The Na₃Ni 2–x Cu x SbO₆ compositions follow an expected transition from an antiferromagnetic ordering to the spin gap of the copper end member. The estimated band gaps for these compounds have been determined from diffuse reflectance measurements. - Graphical abstract: Complete solid solutions with the composition Na₃M 2–x M´ x SbO₆ where M, M´=Cu, Mg, Ni, Zn have been synthesized using conventional solid state techniques and were investigated using X-ray diffraction, magnetism and optical measurements. Based on an ionic radii point of view the lattice parameter shifting in the composition containing copper are opposite of what would be expected. The Cu²⁺ is Jahn–Teller active which distorts the C2/m cell, increasing the β angle between the a and c parameters and explains this shifting pattern. Highlights: • The solid solutions O₃–Na₃M 2–x M´ x SbO₆(M, M´=Cu, Mg, Ni, Zn) were synthesized. • These compounds crystallize in the C2/m space group. • The Jahn–Teller active Cu²⁺ causes distortion of the monoclinic cell. • The Cu²⁺ spin gap magnetic properties are diluted upon 25% substitution. • All compositions are insulating and have large band gaps.