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Self-Assembled Octanuclear [Ni5Ln3] (Ln = Dy, Tb and Ho) Complexes: Synthesis, Coordination Induced Ligand Hydrolysis, Structure and Magnetism

Abstract

The variable coordination behavior of 2-{[(2-hydroxy-3-methoxybenzyl)imino]methyl}-6-methoxyphenol (H2L) and its hydrolyzed congener towards NiCl2∙6H2O and LnIII nitrate salts provide a family of coordination aggregates containing a [Ni5Ln3] octanuclear core structure. Room temperature reactions in MeOH–CHCl3 medium and in the presence of NEt3 yield isostructural [Ni5Ln3(L)4(μ-OH)23-OH)6(o-val)2(H2O)6]NO3•7H2O (Ln = Dy3+ (1), Tb3+ (2), and Ho3+ (3); o-val = o-vanillin) heterometallic complexes. All the three complexes hold an octanuclear fused partial hexacubane topology from the utilization of phenolate-based ligand anions, clipping five 3d and three 4f ions. Direct current magnetic susceptibility measurements showed an upsurge at low temperature for complex 1 and 2, indicative of ferromagnetic interactions while antiferromagnetic exchange interaction predominates for complex 3. AC magnetic susceptibility measurements were not able to show any slow relaxation property to the magnetization. CASSCF calculations for complex 1 indicates all three Dy3+ centres have anisotropic axes but the relative orientation of the magnetic axes reduce the probability of this molecule to behave like a SMM which further established by the POLY_ANISO calculations.

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Supplementary files

Article information


Submitted
08 May 2020
Accepted
14 May 2020
First published
15 May 2020

Dalton Trans., 2020, Accepted Manuscript
Article type
Paper

Self-Assembled Octanuclear [Ni5Ln3] (Ln = Dy, Tb and Ho) Complexes: Synthesis, Coordination Induced Ligand Hydrolysis, Structure and Magnetism

A. Bhanja, E. Moreno Pineda, R. Herchel, W. Wernsdorfer and D. Ray, Dalton Trans., 2020, Accepted Manuscript , DOI: 10.1039/D0DT01675F

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