Inorganics 2018, 6(2), 61; https://doi.org/10.3390/inorganics6020061
Mononuclear Dysprosium(III) Complexes with Triphenylphosphine Oxide Ligands: Controlling the Coordination Environment and Magnetic Anisotropy
Stuart K. Langley 1,*
, Kuduva R. Vignesh 2, Kerey Holton 1, Sophie Benjamin 3
, Gary B. Hix 4, Wasinee Phonsri 5, Boujemaa Moubaraki 5, Keith S. Murray 5,*
and Gopalan Rajaraman 2,*
, Gary B. Hix 4, Wasinee Phonsri 5, Boujemaa Moubaraki 5, Keith S. Murray 5,*
and Gopalan Rajaraman 2,*
1
School of Science and the Environment, Division of Chemistry, Manchester Metropolitan University, Manchester M15 6BH, UK
2
Department of Chemistry, IIT Bombay, Mumbai 400076, India
3
School of Science and Technology, Nottingham Trent University, Nottingham NG11 8NS, UK
4
School of Sciences, University of Wolverhampton, Wolverhampton WV1 1LY, UK
5
School of Chemistry, Monash University, Clayton, VIC 3800, Australia
*
Authors to whom correspondence should be addressed.
Received: 1 May 2018 / Revised: 8 June 2018 / Accepted: 9 June 2018 / Published: 12 June 2018
(This article belongs to the Special Issue Magnetic Lanthanide Complexes)
Abstract
We report the synthesis, structural and magnetic characterization of five mononuclear DyIII ion complexes using triphenylphosphine oxide as a monodentate ligand. They have formulae [DyIII(OPPh3)3(NO3)3] (1), [DyIII(OPPh3)4(NO3)2](NO3) (2), [DyIII(OPPh3)3Cl3] (3), [DyIII(OPPh3)4Cl2]Cl (4) and [DyIII(OPPh3)4Cl2](FeCl4) (5). These complexes are characterized using single crystal X-ray diffraction, which revealed that each complex has a unique coordination environment around the DyIII ion, which results in varying dynamic magnetic behavior. Ab initio calculations are performed to rationalize the observed magnetic behavior and to understand the effect that the ligand and coordination geometry around the DyIII ion has on the single-molecule magnet (SMM) behavior. In recent years, seven coordinate DyIII complexes possessing pseudo ~D5h symmetry are found to yield attractive blocking temperatures for the development of new SMM complexes. However, here we show that the strength of the donor ligand plays a critical role in determining the effective energy barrier and is not simply dependent on the geometry and the symmetry around the DyIII ion. Seven coordinate molecules possessing pseudo D5h symmetry with strong equatorial ligation and weak axial ligation are found to be inferior, exhibiting no SMM characteristics under zero-field conditions. Thus, this comprehensive study offers insight on improving the blocking temperature of mononuclear SMMs. View Full-TextKeywords:
single molecule magnets; single ion magnets; phosphine oxide complexes; lanthanide SMMs; magnetic anisotropy; ab initio calculations
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Langley, S.K.; Vignesh, K.R.; Holton, K.; Benjamin, S.; Hix, G.B.; Phonsri, W.; Moubaraki, B.; Murray, K.S.; Rajaraman, G. Mononuclear Dysprosium(III) Complexes with Triphenylphosphine Oxide Ligands: Controlling the Coordination Environment and Magnetic Anisotropy. Inorganics 2018, 6, 61.
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