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Dalton Trans ; 45(36): 14174-83, 2016 Sep 28.
Artículo en Inglés | MEDLINE | ID: mdl-27530153

RESUMEN

Using a dicarboxylate ligand appended with (2-pyridyl)ethylamine unit, a new cluster [Ni(L(4))6(DMF)2(CH3OH)2(H2O)6][ClO4]4·2CH3OH·2CH3CO2C2H5 (1) [L(4)(2-): 3-[N-{2-(pyridin-2-yl)ethyl}amino]-bis(propionate)] has been synthesized, through 'coordination-driven self-assembly'. The crystal structure of 1 reveals a centrosymmetric octanuclear carboxylate-bridged nickel(ii) tetracation, with a distorted cubane topology. The four crystallographically independent nickel(ii) centres differ markedly in their coordination environment. Magnetic studies (2-300 K) reveal that in 1 the net magnetic-exchange is antiferromagnetic. Based on geometric parameters associated with two interacting nickel(ii) centres, six magnetic-exchange coupling constants (J values) were considered for magnetic data analysis. Notably, 1 provides the first example of a Ni cluster (i) bridged solely by carboxylates in three bridging modes (monatomic, syn-anti and anti-anti), (ii) exhibiting four ferromagnetic and two antiferromagnetic magnetic-interactions and (iii) demonstrating a good agreement between six J values (obtained from experimental data analysis) and those obtained from DFT calculations, at the B3LYP-level of theory.

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