A₂MnXO₄ Family (A = Li, Na, Ag; X = Si, Ge): Structural and Magnetic Properties

Four new manganese germanates and silicates, A₂MnGeO₄ (A = Li, Na) and A₂MnSiO₄ (A = Na, Ag), were prepared, and their crystal structures were determined using the X-ray Rietveld method. All of them contain all components in tetrahedral coordination. Li₂MnGeO₄ is orthorhombic (Pmn2₁) layered, isostructural with Li₂CdGeO₄, and the three other compounds are monoclinic (Pn) cristobalite-related frameworks. As in other stuffed cristobalites of various symmetry (Pn A₂MXO₄, Pna2₁ and Pbca AMO₂), average bond angles on bridging oxygens (here, Mn-O-X) increase with increasing A/X and/or A/M radius ratios, indicating the trend to the ideal cubic (Fd3̅m) structure typified by CsAlO₂. The sublattices of the magnetic Mn²⁺ ions in both structure types under study (Pmn2₁ and Pn) are essentially the same; namely, they are pseudocubic eutaxy with 12 nearest neighbors. The magnetic properties of the four new phases plus Li₂MnSiO₄ were characterized by carrying out magnetic susceptibility, specific heat, magnetization, and electron spin resonance measurements and also by performing energy-mapping analysis to evaluate their spin exchange constants. Ag₂MnSiO₄ remains paramagnetic down to 2 K, but A₂MnXO₄ (A = Li, Na; X = Si, Ge) undergo a three-dimensional antiferromagnetic ordering. All five phases exhibit short-range AFM ordering correlations, hence showing them to be low-dimensional magnets and a magnetic field induced spin-reorientation transition at T < T_N for all AFM phases. We constructed the magnetic phase diagrams for A₂MnXO₄ (A = Li, Na; X = Si, Ge) on the basis of the thermodynamic data in magnetic fields up to 9 T. The magnetic properties of all five phases experimentally determined are well explained by their spin exchange constants evaluated by performing energy-mapping analysis.