Mononuclear dysprosium(III) complexes with triphenylphosphine oxide ligands: controlling the coordination environment and magnetic anisotropy

Langley, S.K., Vignesh, K.R., Holton, K., Benjamin, S.L. ORCID: 0000-0002-5038-1599, Hix, G.B. ORCID: 0000-0002-3784-1562, 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): 61. ISSN 2304-6740

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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.

Item Type: Journal article
Publication Title: Inorganics
Creators: Langley, S.K., Vignesh, K.R., Holton, K., Benjamin, S.L., Hix, G.B., Phonsri, W., Moubaraki, B., Murray, K.S. and Rajaraman, G.
Publisher: MDPI
Date: 12 June 2018
Volume: 6
Number: 2
ISSN: 2304-6740
Identifiers:
NumberType
10.3390/inorganics6020061DOI
inorganics6020061Publisher Item Identifier
Rights: 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).
Divisions: Schools > School of Science and Technology
Depositing User: Jonathan Gallacher
Date Added: 04 Jul 2018 10:22
Last Modified: 04 Jul 2018 10:22
URI: http://irep.ntu.ac.uk/id/eprint/33995

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