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

Bhanja, Avik, Smythe, Lucy, Herchel, Radovan, Nemec, Ivan, Murrie, Mark ORCID: https://orcid.org/0000-0001-7297-2878 and Ray, Debashis(2021) Hydroxido supported and differently networked octanuclear Ni6Ln2 [Ln = GdIII and DyIII] complexes: structural variation, magnetic properties and theoretical insights.Dalton Transactions, 50(14), pp. 5023-5035. (doi: 10.1039/D0DT04168H)

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Abstract

The design and synthesis of Schiff base H2L, (2-{[(2-hydroxy-3-methoxybenzyl)imino]methyl}phenol) bearing 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 provides [Gd2Ni6L4(μ3-OH)6(μ-OH)2(μ-H2O)2(CH3CO2)2(H2O)3(MeOH)]∙8H2O (1), having ‘butterfly−shaped’ core and [Dy2Ni6L4(μ3-OH)4(μ-Cl)2Cl4(H2O)2(MeOH)2]∙2MeOH∙4H2O (2) with ‘candy–shaped’ core. Fusion of six partial cubane units led to mineral-like core in 1, developed around central Ni2(OH)2 moiety; whereas in case of 2, four such partial cubanes are collapsed on Dy2(OH)2. Direct-current (dc) magnetic susceptibility measurements reveal predominantly ferromagnetic interactions leading to a high‒spin S = 13 ground state for 1. Complex 2 exhibits slow relaxation of magnetization in a small applied dc field with an energy barrier to reorientation of the magnetization, Ueff = 19.3 (0.1) K. The static and dynamic magnetic data are analysed and corroborated by density functional theory (DFT) and detailed CASSCF based calculations.

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