RT Journal Article
T1 Dinuclear Fluoride Single-Bridged Lanthanoid Complexes as Molecule Magnets: Unprecedented Coupling Constant in a FluorideBridged Gadolinium Compound
A1 Corredoira Vázquez, Julio
A1 González-Barreira, Cristina
A1 Fondo Busto, María Matilde
A1 García Deibe, Ana María
A1 Sanmartín Matalobos, Jesús
A1 Gómez-Coca, Silvia
A1 Ruíz, Eliseo
A1 Colacio, Enrique
K1 lantanoides
K1 imanes moleculares
K1 fluoruros
AB A new synthetic method allows isolating fluoride-bridged complexesBu4N{[M(3NO2,5Br-H3L1,1,4)]2(μ-F)} (M = Dy, 1; M = Ho, 2; M = Gd, 3) and Bu4N{[Dy(3Br,5Cl-H3L1,2,4)]2(μ-F)}·2H2O, 4·2H2O. The crystal structures of 1· 5CH3C6H5,·2·2H2O·0.75THF, 3, and 4·2H2O·2THF show that all of them are dinuclear compounds with linear single fluoride bridges and octacoordinated metal centers. Magnetic susceptibility measurements in the temperature range of 2−300 K reveal that the GdIII ions in 3 are weakly antiferromagnetically coupled, and this constitutes the first crystallographically and magnetically analyzed gadolinium complex with a fluoride bridge. Variabletemperature magnetization demonstrates a poor magnetocaloric effect for 3. Alternating current magnetic measurements for 1, 2, and 4·2H2O bring to light that 4·2H2O is an SMM, 1 shows an SMM-like behavior under a magnetic field of 600 Oe, while 2 does not show relaxation of the magnetization even under an applied magnetic field. In spite of this, 2 is the first fluoride-bridged holmium complex magnetically analyzed. DFT and ab initio calculations support the experimental magnetic results and show that apparently small structural differences between 1 and 4·2H2O introduce important changes in the dipolar interactions, from antiferromagnetic in 1 to ferromagnetic in 4·2H2O.
PB ACS Publications
YR 2022
FD 2022
LK http://hdl.handle.net/10347/31912
UL http://hdl.handle.net/10347/31912
LA eng
NO Inorg. Chem. 2022, 61, 9946−9959
NO Ministerio de Ciencia e InnovaciónXunta de Galicia
DS Minerva
RD 24 abr 2026