A 2 MnXO 4 Family (A = Li, Na, Ag; X = Si, Ge): Structural and Magnetic Properties

• Published in: Inorganic chemistry 2017-11, Vol.56 (22), p.14023-14039
• Main Authors: Nalbandyan, Vladimir B, Zvereva, Elena A, Shukaev, Igor L, Gordon, Elijah, Politaev, Vladimir V, Whangbo, Myung-Hwan, Petrenko, Aleksandr A, Denisov, Roman S, Markina, Maria M, Tzschoppe, Michael, Bukhteev, Kirill Yu, Klingeler, Rüdiger, Vasiliev, Alexander N
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.7b02130

Four new manganese germanates and silicates, A MnGeO (A = Li, Na) and A MnSiO (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. Li MnGeO is orthorhombic (Pmn2 ) layered, isostructural with Li CdGeO , and the three other compounds are monoclinic (Pn) cristobalite-related frameworks. As in other stuffed cristobalites of various symmetry (Pn A MXO , Pna2 and Pbca AMO ), 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 CsAlO . The sublattices of the magnetic Mn ions in both structure types under study (Pmn2 and Pn) are essentially the same; namely, they are pseudocubic eutaxy with 12 nearest neighbors. The magnetic properties of the four new phases plus Li MnSiO 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. Ag MnSiO remains paramagnetic down to 2 K, but A MnXO (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 for all AFM phases. We constructed the magnetic phase diagrams for A MnXO (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.