Mononuclear dysprosium (III) complexes with triphenylphosphine oxide ligands: Controlling the coordination environment and magnetic anisotropy
Authors
Langley, Stuart K.Vignesh, Kuduva R.
Holton, Kerey
Benjamin, Sophie
Hix, Gary B.
Phonsri, Wasinee
Moubaraki, Boujemaa
Murray, Keith S.
Rajaraman, Gopalan
Issue Date
2018-06-12
Metadata
Show full item recordAbstract
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.Citation
Langley, S.K., Vignesh, K.R., Holton, K., Benjamin, S.L., Hix, G.B., Phonsri, W., Moubaraki, B., Murray, K.S. and Rajaraman, G. (2018) 'Mononuclear dysprosium (III) complexes with triphenylphosphine oxide ligands: Controlling the coordination environment and magnetic anisotropy', Inorganics, 6 (2) doi: 10.3390/inorganics6020061Publisher
MDPIJournal
InorganicsAdditional Links
http://www.mdpi.com/2304-6740/6/2/61Type
Journal articleLanguage
enDescription
© 2018 The Authors. Published by MDPI. This is an open access article available under a Creative Commons licence. The published version can be accessed at the following link on the publisher’s website: https://doi.org/10.3390/inorganics6020061ISSN
2304-6740ae974a485f413a2113503eed53cd6c53
10.3390/inorganics6020061
Scopus Count
Collections
The following licence applies to the copyright and re-use of this item:
- Creative Commons
Except where otherwise noted, this item's license is described as https://creativecommons.org/licenses/by/4.0/