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Issue 14, 2021
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Hydroxido supported and differently networked octanuclear Ni6Ln2 [Ln = GdIII and DyIII] complexes: structural variation, magnetic properties and theoretical insights

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Abstract

The design and synthesis of a Schiff base H2L, (2-{[(2-hydroxy-3-methoxybenzyl)imino]methyl}phenol), bearing an ONOO donor set has been explored for its reactivity pattern with LnCl3·6H2O (Ln = GdIII and DyIII) and Ni(CH3CO2)2·4H2O in the presence of NEt3 for molecular aggregation. Coordination driven spontaneous self-assembly reactions provide [Gd2Ni6L43-OH)6(μ-OH)2(CH3CO2)2(μ-H2O)2(H2O)3(MeOH)]·8H2O (1) having a ‘butterfly-shaped’ core and [Dy2Ni6L43-OH)4(μ-Cl)2Cl4(H2O)2(MeOH)2]·2MeOH·4H2O (2) with a ‘candy-shaped’ core. Fusion of six partial cubane units led to a mineral-like core in 1, developed around the central Ni2(OH)2 moiety, whereas in the case of 2, four such partial cubanes collapsed on Dy2(OH)2. Direct-current (dc) magnetic susceptibility measurements revealed that predominant ferromagnetic interactions lead to a high-spin S = 13 ground state for 1. Complex 2 exhibits slow relaxation of magnetization under an applied small dc field with an energy barrier to reorientation of the magnetization, Ueff = 19.3 K. The static and dynamic magnetic data are analysed and corroborated by density functional theory (DFT) and detailed CASSCF based calculations.

Graphical abstract: Hydroxido supported and differently networked octanuclear Ni6Ln2 [Ln = GdIII and DyIII] complexes: structural variation, magnetic properties and theoretical insights

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Article information


Submitted
07 Dec 2020
Accepted
09 Mar 2021
First published
10 Mar 2021

Dalton Trans., 2021,50, 5023-5035
Article type
Paper

Hydroxido supported and differently networked octanuclear Ni6Ln2 [Ln = GdIII and DyIII] complexes: structural variation, magnetic properties and theoretical insights

A. Bhanja, L. Smythe, R. Herchel, I. Nemec, M. Murrie and D. Ray, Dalton Trans., 2021, 50, 5023
DOI: 10.1039/D0DT04168H

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