RT Journal Article T1 Magnetic transitions and isotropic versus anisotropic magnetic behaviour of [CH3NH3][M(HCOO)3] M = Mn2+, Co2+, Ni2+, Cu2+ metal–organic perovskites A1 Pato Doldán, Breogán A1 Gómez Aguirre, Lilián Claudia A1 Hansen, Anders P. A1 Mira Pérez, Jorge A1 Castro García, Socorro A1 Sánchez Andújar, Manuel A1 Señarís Rodríguez, María Antonia A1 Zapf, Vivien A1 Singleton, John AB Here we present an in-depth study of the magnetic properties of a family of metal–organic perovskites ABX3, [CH3NH3][M(HCOO)3] in which A = CH3NH3+ is the methylammonium cation, B = M is a divalent metal cation (Mn2+, Co2+, Ni2+ or Cu2+), and X is the formate anion (HCOO−). The magnetic properties have been measured on powdered samples and along the different orientations of mm-sized single crystals. They display spin-canted weak ferromagnetism with Néel temperatures of 8.0 K (Mn2+), 15.7 K (Co2+) and 34 K (Ni2+), which are inversely proportional to the ionic radii of the metal cations. The Cu2+ member displays low-dimensional magnetism as a result of orbital ordering of the Cu2+ d orbitals originating from a Jahn–Teller distortion. Pulsed-field magnetization experiments (fields of up to 60 T at temperatures down to 0.6 K) show that Mn2+, Co2+ and Ni2+ formates display cation-characteristic spin flop transitions. A saturation magnetization value of 5 μB (at 12.5 T) was observed for Mn2+, meanwhile the Co2+ formate shows an orientation dependent quasi saturation (5.1 μB at 21 T along [101] vs. 5.8 μB at 26 T along [010]). The different isotropic/anisotropic behaviour can be explained by the orbital contribution to the magnetic response PB Royal Society of Chemistry YR 2016 FD 2016 LK http://hdl.handle.net/10347/24334 UL http://hdl.handle.net/10347/24334 LA eng NO J. Mater. Chem. C, 2016,4, 11164-11172 NO The Spanish authors are grateful for financial support from Ministerio de Economía y Competitividad (MINECO) (Spain) and EU under the project ENE2014-56237-C4-4-R, and Xunta de Galicia under the project GRC2014/042. L. C. G.-A. acknowledges UDC for a predoctoral fellowship and Fundación Barrié for the research stay grant at LANL. Work at LANL, A. P. H. and B. P.-D.'s visit to LANL were funded by the Laboratory Directed Research and Development program at LANL. The NHMFL pulsed-field facility is funded by the U.S. National Science Foundation through Cooperative Grant No. DMR-1157490, the State of Florida, and the U.S. Department of Energy DS Minerva RD 28 abr 2026