Influence of the Ligand Field on the Slow Relaxation of Magnetization of Unsymmetrical Monomeric Lanthanide Complexes: Synthesis and Theoretical Studies

Apoorva Upadhyay, Kuduva R. Vignesh, Chinmoy Das, Saurabh Kumar Singh, Gopalan Rajaraman, Maheswaran Shanmugam

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21 Scopus citations

Abstract

A series of monomeric lanthanide Schiff base complexes with the molecular formulas [Ce(HL)3(NO3)3] (1) and [Ln(HL)2(NO3)3], where LnIII = Tb (2), Ho (3), Er (4), and Lu (5), were isolated and characterized by single-crystal X-ray diffraction (XRD). Single-crystal XRD reveals that, except for 1, all complexes possess two crystallographically distinct molecules within the unit cell. Both of these crystallographically distinct molecules possess the same molecular formula, but the orientation of the coordinating ligand distinctly differs from those in complexes 2-5. Alternating-current magnetic susceptibility measurement reveals that complexes 1-3 exhibit slow relaxation of magnetization in the presence of an optimum external magnetic field. In contrast to 1-3, complex 4 shows a blockade of magnetization in the absence of an external magnetic field, a signature characteristic of a single-ion magnet (SIM). The distinct magnetic behavior observed in 4 compared to other complexes is correlated to the suitable ligand field around a prolate ErIII ion. Although the ligand field stabilizes an easy axis of anisotropy, quantum tunnelling of magnetization (QTM) is still predominant in 4 because of the low symmetry of the complex. The combination of low symmetry and an unsuitable ligand-field environment in complexes 1-3 triggers faster magnetization relaxation; hence, these complexes exhibit field-induced SIM behavior. In order to understand the electronic structures of complexes 1-4 and the distinct magnetic behavior observed, ab initio calculations were performed. Using the crystal structure of the complexes, magnetic susceptibility data were computed for all of the complexes. The computed susceptibility and magnetization are in good agreement with the experimental magnetic data [XMT(T) and M(H)] and this offers confidence on the reliability of the extracted parameters. A tentative mechanism of magnetization relaxation observed in these complexes is also discussed in detail.

Original languageEnglish (US)
Pages (from-to)14260-14276
Number of pages17
JournalInorganic chemistry
Volume56
Issue number22
DOIs
StatePublished - Nov 20 2017

Bibliographical note

Funding Information:
M.S. thanks the funding agencies SERB (EMR/2015/000592) INSA (SP/YSP/119/2015/1264), and IRCC-IIT Bombay for financial support. G.R. acknowledges SERB (EMR/2014/ 000247) and INSA for funding. A.U. extends her sincere thanks to CSIR and IRCC for fellowship.

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