Field-Induced Single Molecule Magnets of Phosphine- and Arsine-Oxides
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Fondo, Matilde; Corredoira-Vázquez, Julio; García-Deibe, Ana M.; Sanmartín-Matalobos, Jesús; Herrera Martínez, Juan Manuel; Colacio Rodríguez, EnriqueEditorial
Frontiers Media
Materia
Terbium Dysprosium Triphenylarsine oxide Phosphine oxide Single ion magnet
Date
2018-09-12Referencia bibliográfica
Fondo M, Corredoira-Vázquez J, García-Deibe AM, Sanmartín-Matalobos J, Herrera JM and Colacio E (2018) Field-Induced Single Molecule Magnets of Phosphine- and Arsine-Oxides. Front. Chem. 6:420. [doi: 10.3389/fchem.2018.00420]
Sponsorship
Financial support from Ministerio de Economía y Competitividad (MINECO, CTQ2014-56312-P), Junta de Andalucía (FQM-195 and Project of excellence P11-FQM-7756) and the University of Granada are grateful acknowledged. JC-V acknowledges Xunta de Galicia for his Ph.D. fellowship.Abstract
The coordination chemistry of dysprosium and terbium toward phosphine and arsine
oxides was further explored. Thus, the new nitrate [M(NO3)3(Ph3PO)3] (M = Tb,
1; Dy, 2), [Dy(NO3)3(EtOH)(Ph3XO)2] (X = P, 3; As, 4), chloride [DyCl2(Ph3AsO)4]Cl
(5), triflate [Dy(OTf)2(MePh2PO)4]OTf (6; OTf = triflate) and hexafluoroacetylacetonate
[M(hfa)3(Ph3PO)2] (hfa = hexafluoroacetylacetonate; M = Tb, 7; Dy, 8) complexes
were isolated and fully characterized. The crystal structures of 1·CH3CN, 2·CH3CN, 4,
5·2.75EtOH·1.25H2O, 6, 7, and 8 show MO9 cores in 1, 2, and 4, with highly distorted
geometry, between spherical capped square antiprism and muffin-like, hexacoordinated
environments for the dysprosium ions in 5 and 6, with octahedral geometry, and octacoordination
for the lanthanoid metals in 7 and 8, with geometry closer to square
antiprism. Comparison of the magnetic behavior of all the complexes allows analyzing
which metal ion (Tb or Dy), phosphine or arsine oxide, or anionic ligand favor more the
slow relaxation of the magnetization. Alternating current magnetic measurements show
that only 2, 4, and 8 present slow relaxation of the magnetization in the presence of
an external magnetic field, 8 being the complex with the highest Ueff (44.85 K) of those
described herein.