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Zinc-diluted magnetic metal formate perovskites: synthesis, structures, and magnetism of [CH3NH3][Mn(x)Zn(1-x)(HCOO)3] (x = 0-1).

The preparation, structures, and magnetic properties of a series of metal formate perovskites [CH(3)NH(3)][Mn(x)Zn(1-x)(HCOO)(3)] were investigated. The isostructural solid solution can be prepared in the complete range of x=0-1. The metal-organic perovskite structures consist of an anionic NaCl type [Mn(x)Zn(1-x)(HCOO)(3)(-)] framework with CH(3)NH(3)(+) templates located in the nearly cubic cavities and forming hydrogen bonds to the framework. When the proportion of Mn increased (i.e., x changed from 0 to 1), the lattice dimensions and metal-oxygen and metal-metal distances show a slight, nonlinear increase because of the increased averaged metal ionic radius and the local structure distortion. Through the series, the magnetism changes from the long-range ordering of spin-canted antiferromagnetism for x≥0.40 to paramagnetism when x≤0.30, and the percolation limit was estimated to be x(P)=0.31(2) for this simple cubic lattice. In the low-temperature region, enhancement of magnetization and the gradual decrease and final disappearance of coercive field, remnant magnetization, and spin-flop field upon dilution were observed through this isotropic Heisenberg magnetic series. IR spectroscopic and thermal properties were also investigated.