RT Journal Article
T1 Eight coordinated mononuclear dysprosium complexes of heptadentate aminophenol ligands: the influence of the phenol substituents and the ancillary donors on the magnetic relaxation
A1 Fondo Busto, María Matilde
A1 Corredoira Vázquez, Julio
A1 García Deibe, Ana María
A1 Sanmartín Matalobos, Jesús
A1 Reta, Daniel
A1 Colacio, Enrique
K1 dysprosium
K1 phenol substituents
K1 magnetic relaxation
AB The mononuclear complexes [Dy(3Br,5Cl-H3L1,1,4)(D)]·solvate (D = H2O, solvate = 0.25MeOH, 1W·0.25MeOH; D = Py without solvate, 1Py), and [Dy(3NO2,5Br-H3L1,1,4)(H2O)] (2W) were isolated. The crystal structures of 1W·0.25MeOH, 1Py and 2W·2CH3C6H5 show that the DyIII ion is octacoordinated, in N4O4 or N5O3 environments, with distorted geometries, between square antiprism, biaugmented trigonal prism and triangular dodecahedral. A similar environment for the metal ion is shown in the chiral crystals of the diamagnetic yttrium analogue [Y(3Br,5Cl-H3L1,1,4)(MeOH)] (3M), which were spontaneously resolved. Magnetic analyses of the three dysprosium complexes, and their diluted analogous 1W@Y, 1Py@Y and 2W@Y, reveal that none of them seem to relax through an Orbach mechanism at Hdc = 0. However, the three complexes show Orbach relaxation under Hdc = 1000 Oe, and 1Py is the in-field SIM with the highest energy barrier among these complexes, with a Ueff value of 358 K. Analysis of ac magnetic data shows that the electron-withdrawing substituents on the phenol rings of the aminophenol ligands, as well as the auxiliary oxygen donors from water ligands, reduce the energy barriers of the complexes, which is attributed to a charge reduction in the coordinating atoms of the aminophenol donor. Ab initio calculations support the experimental results.
PB The Royal Society of Chemistry
YR 2021
FD 2021
LK http://hdl.handle.net/10347/32390
UL http://hdl.handle.net/10347/32390
LA eng
NO Fondo, M., Julio Corredoira-Vázquez, J., García-Deibe, A.M., Sanmartín-Matalobos, J., Reta, D., Colacio, E. (2021). Eight coordinated mononuclear dysprosium complexes of heptadentate aminophenol ligands: the influence of the phenol substituents and the ancillary donors on the magnetic relaxation. "Dalton Transactions", vol. 50, n. 43, 15878-15887
NO Authors thank the Spanish Ministerio de Innovación, Ciencia y Universidades (PGC2018 102052-B-C21) and Xunta de Galicia for financial support. J. C. V also thanks Xunta de Galicia for his Ph.D. fellowship. The authors acknowledge computer resources, technical expertise and assistance provided by the CESGA.
DS Minerva
RD 28 abr 2026