Next Article in Journal
Heteroleptic Iron(III) Spin Crossover Complexes; Ligand Substitution Effects
Next Article in Special Issue
Magnetochemistry: From Fundamentals to Applications
Previous Article in Journal / Special Issue
A Spin Crossover Transition in a Mn(II) Chain Compound
Article Menu

Export Article

Open AccessArticle
Magnetochemistry 2016, 2(1), 2; doi:10.3390/magnetochemistry2010002

Key Role of Size and Electronic Configuration on the Sign and Strength of the Magnetic Coupling in a Series of Cu2Ln Trimers (Ln = Ce, Gd, Tb, Dy and Er)

1
Department of Chemistry, University College of Science, University of Calcutta, 92, APC Road, Kolkata 700009, India
2
Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán, 2. 46980 Paterna, Valencia, Spain
*
Author to whom correspondence should be addressed.
Academic Editor: Martin T. Lemaire
Received: 1 December 2015 / Revised: 16 December 2015 / Accepted: 18 December 2015 / Published: 29 December 2015
(This article belongs to the Special Issue Magnetochemistry: From Fundamentals to Applications)
View Full-Text   |   Download PDF [1253 KB, uploaded 29 December 2015]   |  

Abstract

Five new trinuclear complexes with formula [(CuLα−Me)2Ce(NO3)3] (1) and [(CuLα−Me)2Ln(H2O)(NO3)2](NO3)·2(CH3OH) (Ln = Gd(2), Tb(3), Dy(4) and Er(5)) have been synthesized using the bidentate N2O2 donor metalloligand [CuLα−Me] (H2Lα−Me = N,N′-bis(α-methylsalicylidene)-1,3-propanediamine) and structurally characterized. In the case of compound 1, the larger ionic radius of Ce(III) leads to a neutral trinuclear complex with an asymmetric CeO10 tetradecahedron coordination geometry formed by four oxygen atoms from two (CuLα−Me) units and three bidentate NO3 ligands. In contrast, the isomorphic complexes 25, with smaller Ln(III) ions, give rise to monocationic trinuclear complexes with a non-coordinated nitrate as a counter ion. In these complexes, the Ln(III) ions show a LnO9 tricapped trigonal prismatic coordination geometry with C2 symmetry formed by four oxygen atoms from two (CuLα−Me) units, two bidentate NO3 ligands and a water molecule. The magnetic properties show the presence of weak antiferromagnetic interactions in 1 and weak ferromagnetic interactions in 25. The fit of the magnetic properties of compounds 25 to a simple isotropic-exchange symmetric trimer model, including the anisotropy of the Ln(III) ions, shows that in all cases the Cu-Ln magnetic coupling is weak (JCu-Ln = 1.81, 1.27, 0.88 and 0.31 cm−1 for 25, respectively) and linearly decreases as the number of unpaired f electrons of the Ln(III) decreases. The value found in compound 2 nicely fits with the previously established correlation between the dihedral Cu–O–O–Gd angle and the J value. View Full-Text
Keywords: 3d-4f complexes; crystal structure; magnetic properties; coupling constants; magnetostructural correlations; lanthanide series 3d-4f complexes; crystal structure; magnetic properties; coupling constants; magnetostructural correlations; lanthanide series
Figures

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 materials

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

MDPI and ACS Style

Ghosh, S.; Gómez García, C.J.; Clemente-Juan, J.M.; Ghosh, A. Key Role of Size and Electronic Configuration on the Sign and Strength of the Magnetic Coupling in a Series of Cu2Ln Trimers (Ln = Ce, Gd, Tb, Dy and Er). Magnetochemistry 2016, 2, 2.

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]
Magnetochemistry EISSN 2312-7481 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top