Next Article in Journal
Erratum: Knoblauch, N. et al. Ceria: Recent Results on Dopant-Induced Surface Phenomena . Inorganics 2017, 5, 76
Next Article in Special Issue
Chiral, Heterometallic Lanthanide–Transition Metal Complexes by Design
Previous Article in Journal
The Effect of Illumination Direction and Temperature on Dye-Sensitized Solar Cells with Viscous Cobalt Complex-Based Electrolytes
Article Menu
Issue 2 (June) cover image

Export Article

Open AccessArticle
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

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)
Full-Text   |   PDF [6164 KB, uploaded 15 June 2018]   |  

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-Text
Keywords: single molecule magnets; single ion magnets; phosphine oxide complexes; lanthanide SMMs; magnetic anisotropy; ab initio calculations single molecule magnets; single ion magnets; phosphine oxide complexes; lanthanide SMMs; magnetic anisotropy; ab initio calculations
Figures

Graphical abstract

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

Supplementary material

SciFeed

Share & Cite This Article

MDPI and ACS Style

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.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Inorganics EISSN 2304-6740 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top