Premium
The Missing Link in the Magnetism of Hybrid Cobalt Layered Hydroxides: The Odd–Even Effect of the Organic Spacer
Author(s) -
Oestreicher Víctor,
Hunt Diego,
Dolle Christian,
Borovik Paula,
Jobbágy Matías,
Abellán Gonzalo,
Coronado Eugenio
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003593
Subject(s) - alkyl , magnetism , covalent bond , materials science , hybrid material , octahedron , molecule , crystallography , density functional theory , cobalt , magnetization , condensed matter physics , chemistry , nanotechnology , computational chemistry , organic chemistry , physics , magnetic field , quantum mechanics , crystal structure , metallurgy
A dramatic change in the magnetic behaviour, which solely depends on the parity of the organic linker molecules, has been found in a family of layered Co II hydroxides covalently functionalized with dicarboxylic molecules. These layered hybrid materials have been synthesized at room temperature using a one‐pot procedure through the epoxide route . While hybrids connected by odd alkyl chains exhibit coercive fields (H c ) below ca. 3500 Oe and show spontaneous magnetization at temperatures (T M ) below 20 K, hybrids functionalized with even alkyl chains behave as hard magnets with H c >5500 Oe and display a T M higher than 55 K. This intriguing behaviour was studied by density functional theory with the incorporation of a Hubbard term (DFT+U) calculations, unveiling the structural subtleties underlying this observation. Indeed, the different molecular orientation exhibited by the even/odd alkyl chains, and the orientation of the covalently linked carboxylic groups modify the intensity of the magnetic coupling of both octahedral and tetrahedral in‐plane sublattices, thus strongly affecting the magnetic properties of the hybrid. These findings offer an outstanding level of tuning in the molecular design of hybrid magnetic materials based on layered hydroxides.