RT Journal Article
T1 Influence of Proton Conducting Cations on the Structure and Properties of 2D Anilate-Based Magnets
A1 Palacios Corella, Mario
A1 Fernández Espejo, Alejandro
A1 Bazaga-García, Montse
A1 Ramírez-Losilla, Enrique
A1 Cabeza-Díaz, Aurelio
A1 Clemente-León, Miguel
A1 Coronado, Eugenio
K1 Imanes superconductores
K1 Espectroscopía
K1 Aniones
AB The syntheses, structures, magnetic, and proton conductivity properties of a family of bimetallic anilate-based compounds with inserted alkylammonium cations are presented. The structures of (Me2NH2)[MnIICrIII(Br2An)3]·2H2O (1), (Et2NH2)[MnIICrIII(Br2An)3] (2), (Et3NH)[MnIICrIII(Cl2An)3] (3), and [(Et)(i-Pr)2NH]-[MnIICrIII(Br2An)3]·(CHCl3)0.5·(H2O) (4) contain a 2D anionic network formed by Mn(II) and Cr(III) ions linked through anilate ligands. In 1, 2, and 3, the hexagonal holes of this network are occupied by Me2NH2+, Et2NH2+, or Et3NH+ cations. Interestingly, the small increase of size of the templating cation in 4 ([(Et)(i-Pr)2NH]+ in the place of Me2NH2+, Et2NH2+ or Et3NH+), gives rise to a different structure with half of the cations placed within the layers and the other one in the space between the layers. This leads to bilayers with an interlayer separation similar to those of 1, 2, and 3 separated by larger interbilayer distances. Compounds 1, 2, and 3 show a ferrimagnetic ordering with a Tc of 8.0 K (1), 8.9 K (2), and 8.0 K (3). In 4, the presence of different interlayer distances leads to a metamagnetic behavior when the sample is measured in contact with the mother liquor. The behavior changes in the dry sample, which shows a ferrimagnetic ordering as that of 1, 2, and 3 due to collapse of the structure as confirmed by powder X-ray diffraction. Interestingly, the metamagnetic behavior is recovered after reimmersing the crystals in the mother liquor proving the reversibility of the process. All solids are Grotthuss-type proton conductors with conductivity values ranging between 2.3 × 10−6 S·cm−1 for 3 and 2.4 × 10−5 S·cm−1 for 1 measured at 70 °C and 95% relative humidity and activation energies of ∼0.2 eV.
PB ACS publications
YR 2017
FD 2017-11-01
LK https://hdl.handle.net/10630/20985
UL https://hdl.handle.net/10630/20985
LA eng
NO Inorg. Chem. 2017, 56, 22, 13865–13877
NO EU (ERC Advanced Grant SPINMOL)CTQ2014-52758-P, MAT-2014-56143-R y MAT2016-77648-R del MINECO Unidad de Excelencia María de Maeztu MDM-2015-0538 de la Generalitat ValencianaP12-FQM-1656 de la Junta de Andalucía
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 21 ene 2026