S-shaped decanuclear heterometallic [Ni8Ln2] complexes [Ln(III) = Gd, Tb, Dy and Ho]: theoretical modeling of the magnetic properties of the gadolinium analogue.

Content Provider	Semantic Scholar
Author	Hossain, Sakiat Das, Sourav Chakraborty, Amit K. Lloret, Francesc Cano, Joan Pardo, Emilio Chandrasekhar, Vadapalli
Copyright Year	2014
Abstract	The reaction of 8-quinolinol-2-carboaldoxime (LH2) with Ni(II) and Ln(III) salts afforded the heterometallic decanuclear compounds [Ni8Dy2(μ3-OH)2(L)8(LH)2(H2O)6](ClO4)2·16H2O (1), [Ni8Gd2(μ3-OH)2(L)8(LH)2(H2O)4(MeOH)2](NO3)2·12H2O (2), [Ni8Ho2(μ3-OH)2(L)8(LH)2(H2O)4(MeOH)2](ClO4)2·2MeOH·12H2O (3) and [Ni8Tb2 (μ3-OH)2(L)8(LH)2(MeOH)4(OMe)2]·2CH2Cl2·8H2O (4). While compounds 1-3 are dicationic, compound 4 is neutral. These compounds possess an S-shaped architecture and comprise a long chain of metal ions bound to each other. In all the complexes, the eight Ni(II) and two Ln(III) ions of the multimetallic ensemble are hold together by two μ3-OH, eight dianionic (L(2-)) and two monoanionic oxime ligands (LH(-)) whereas compound 4 has two μ3-OH, eight dianionic (L(2-)), two monoanionic oxime ligands (LH(-)) and two terminal methoxy (MeO(-)) ligands. The central portion of the S-shaped molecular wire is made up of an octanuclear Ni(II) ensemble which has at its two ends the Ln(III) caps. Magnetic studies on 1-4 reveal that the magnetic interactions between neighboring metal ions are negligible at room temperature. On the other hand, at lower temperatures in all the compounds anti-ferromagnetic interactions seem to be dominated. Analysis of the magnetic data for the Gd(III) derivative indicates Ni(II)-Ni(II) anti-ferromagnetic interactions and Gd(III)-Ni(II) ferromagnetic interactions at low temperatures. A theoretical density functional study on the magnetic behavior of the Gd(III) derivative suggests that while the weak ferromagnetic interaction between Gd(III) and Ni(II) is in line with the expectation of the magnetic interactions between orthogonal d and f orbitals, antiferromagnetic Ni(II)-Ni(II) interactions are related to the wide Ni-O-Ni angles (∼102°) and quasi-planar conformation of the Ni2O2 core.
File Format	PDF HTM / HTML
DOI	10.1039/c4dt00465e
PubMed reference number	24876072
Journal	Medline
Volume Number	43
Issue Number	26
Alternate Webpage(s)	http://www.rsc.org/suppdata/dt/c4/c4dt00465e/c4dt00465e1.pdf
Alternate Webpage(s)	https://doi.org/10.1039/c4dt00465e
Journal	Dalton transactions
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article