title: Influence of the supramolecular architecture on the magnetic properties of a Dy(III) single-molecule magnet: an ab initio investigation.
abstract: Single-crystal angular-resolved magnetometry and wavefunction-based calculations have been used to reconsider the magnetic properties of a recently reported Dy(III)-based single-molecule magnet, namely [Dy(hfac)3(L(1))] with hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate and L(1) = 2-(4,5-bis(propylthio)-1,3-dithiol-2-ylidene)-6-(pyridin-2-yl)-5H-[1,3]dithiolo[4',5':4,5]benzo[1,2-d]imidazole. The magnetic susceptibility and magnetization at low temperature are found to be strongly influenced by supramolecular interactions. Moreover, taking into account the hydrogen-bond networks in the calculations allows to explain the orientation of the magnetic axes. This strongly suggests that hydrogen bonds play an important role in the modulation of the electrostatic environment around the Dy(III) center that governs the nature of its magnetic ground-state and the orientation of its anisotropy axes. We thus show here that SMM properties that rely on supramolecular organization may not be transferable into single-molecule devices.
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS - Université de Rennes 1, 263 Avenue du Général Leclerc, 35042 Rennes Cedex, France.
authors.forename: Julie
authors.initials: J
authors.lastname: Jung
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS - Université de Rennes 1, 263 Avenue du Général Leclerc, 35042 Rennes Cedex, France.
authors.forename: Olivier
authors.initials: O
authors.lastname: Cador
authors.affiliation: INSA, ISCR, UMR 6226, Université Européenne de Bretagne, 35708 Rennes, France.
authors.forename: Kevin
authors.initials: K
authors.lastname: Bernot
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS - Université de Rennes 1, 263 Avenue du Général Leclerc, 35042 Rennes Cedex, France.
authors.forename: Fabrice
authors.initials: F
authors.lastname: Pointillart
authors.affiliation: Instituto de Ciencia de Materiales de Aragon, CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain ; Centro Universitario de la Defensa, Academia General Militar, Zaragoza, Spain.
authors.forename: Javier
authors.initials: J
authors.lastname: Luzon
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS - Université de Rennes 1, 263 Avenue du Général Leclerc, 35042 Rennes Cedex, France.
authors.forename: Boris
authors.initials: B
authors.lastname: Le Guennic
keywords: ab initio calculations; dysprosium; magnetic properties; single-molecule magnets; supramolecular effects