Supercritical hydrothermal synthesis, thermal, spectroscopic and magnetic studies of two new polymorphs of Mn(SeO3)

Abstract

Two new manganese(II) selenite polymorphs with formula Mn(SeO₃) have been synthesised using supercritical hydrothermal conditions. The crystal structure of both compounds (1) and (2) has been solved from single-crystal X-ray diffraction data. The structures consist of a three-dimensional framework formed by MnO₆ octahedra and (SeO₃)²⁻ selenite anions with trigonal pyramidal geometry. Compound (1) shows chains of elongated, corner-sharing MnO₆ octahedra. These chains are linked alternately by Mn₂O₁₀ dimers of edge-sharing octahedra. Conversely, compound (2) exhibits MnO₆ octahedra sharing edges with three further octahedra, giving rise to a complex three-dimensional framework. The IR spectra show the characteristic bands of the selenite anion. Studies of luminescence and diffuse reflectance spectroscopy, performed at 6 K and at room temperature, respectively, have been carried out for both compounds. The Dq and Racah parameters are Dq = 830, B = 500 and C = 3790 cm⁻¹ for (1) and Dq = 795, B = 520 and C = 3785 cm⁻¹ for (2). The EPR spectra of both compounds are isotropic with a g-value of 1.99(1), which remains unchanged with variation in temperature. Magnetic measurements indicate the presence of antiferromagnetic couplings as the major interactions in both phases, but with compound (2) exhibiting at low temperature a canting of antiferromagnetically aligned spins. The estimated J-exchange parameters are J/k = −2.2 and −1.93 for (1) and (2), respectively, with J′ = −0.87 and −0.55 K.