Chinmoy Das

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

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 [χMT(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.

Synthesis and magnetic properties of a 1-D helical chain derived from a Nickel-Sodium Schiff base complex

AbstractThe reaction of the deprotonated form of the Schiff base ligand; (E)-2-methoxy-6-((phenylimino) methyl)phenol (L) with nickel chloride hydrate results in the formation of the 1-dimentional coordination polymer; Na[Ni(L)2(OMe)(MeOH)]n (1). The structure was determined via single crystal X-ray diffraction measurements. A careful analysis of the complex shows that the polymer exists as a helical structure, where the helicity is brought about by the presence of an alkali metal ion which is observed for the first time. Moreover the helical structure in 1 is maintained predominantly through covalent bond rather than supramolecular interactions. Direct current magnetic susceptibility measurement suggests that complex 1 obeys the Curie law. The fitting of magnetic data using the PHI software package yields parameters of S = 1, g = 2.26 and D = +4.51 (or D = −7.24 cm−1) for 1. Graphical AbstractWe report a 1-D helical chain of Nickel Schiff base complexes whose helicity is brought by a sodium ion in the crystal lattice. Preliminary magnetic behavior suggests that there is no super-exchange interaction between the nickel ions via a closed shell sodium ion.