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Field-Induced Single Molecule Magnets of Phosphine- And Arsine-Oxides

Field-Induced Single Molecule Magnets of Phosphine- And Arsine-Oxides

Matilde Fondo, Julio Corredoira-Vázquez, Ana M García-Deibe, Jesús Sanmartín-Matalobos, Juan Manuel Herrera, Enrique Colacio

Front Chem. 2018 Sep 12;6:420.

PMID: 30258840

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 octa-coordination 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 U eff (44.85 K) of those described herein.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP1153055	Triphenylarsine oxide		1153-05-5	Price

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