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Dinuclear nickel complexes with a NiO core: A structural and magnetic study

Dalton Transactions, ISSN: 1477-9226, Issue: 35, Page: 4260-4270
2006
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The acetylacetonate complexes [NiL(acac)(MeOH)] ·HO, 1·HO and [NiL (acac)(MeOH)]·1.5HO, 2·1.5HO (HL = (2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)- 3-azabut-3-enyl]-1,3-imidazolidine and HL = (2-(5-bromo-2-hydroxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxyphenyl) -3-azabut-3-enyl]-1,3-imidazolidine) were prepared and fully characterised. Their crystal structures show that they are dinuclear complexes, extended into chains by hydrogen bond interactions. These compounds were used as starting materials for the isolation of the corresponding [NiHL (o-OCCHCO)(H O)]·nMeOH and [NiHL(O CCHCO)(HO)]·nH O dicarboxylate complexes (x = 1, 3; n = 1-3). The crystal structures of [NiHL(o-OCCH CO)(HO)]·MeOH, 3·MeOH, [NiHL(o-OCCHCO )(HO)]·3MeOH, 4·3MeOH and [Ni HL(OCCHCO)(H O)]·2.5HO·0.25MeOH·MeCN, 5·2.5HO·0.25MeOH·MeCN, were solved. Complexes 3-5 show dinuclear [NiHL(dicarboxylate)(HO)] units, expanded through hydrogen bonds that involve carboxylate and water ligands, as well as solvate molecules. The variable temperature magnetic susceptibilities of all the complexes show an intramolecular ferromagnetic coupling between the Ni(ii) ions, which is attempted to be rationalized by comparison with previous results and in the light of molecular orbital treatment. Magnetisation measurements are in accord with a S = 2 ground state in all cases. © The Royal Society of Chemistry 2006.

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