Nickel pivalate complexes: structural variations and magnetic susceptibility and inelastic neutron scattering studies

G Chaboussant, R Basler, H U Gudel, S Ochsenbein, A Parkin, S Parsons, G Rajaraman, A Sieber, A A Smith, G A Timco, R E P Winpenny

Research output: Contribution to journalArticlepeer-review

Abstract

The synthesis and structural characterisation of three small nickel(II) cages are reported, all stabilised by pivalate ligands. The magnetic properties of the cages have been studied by a combination of susceptibility measurements and inelastic neutron scattering. For a dinuclear cage, [Ni-2(mu-OH2)(O2CCMe3)(4)(HO2CCMe3)(4)] 1 the ground state is S=2, with a ferromagnetic exchange interaction between the Ni(II) centres of J=0.32 meV and D-S=2=-0.09 meV in the ground state. For a tetranuclear heterocubane cage, [Ni-4(mu(3)-OMe)(4)(O2CCMe3)(4)(MeOH)(4)](2), two ferromagnetic exchange interactions are found and an S= 4 ground state observed. While the zero-field splitting of this state cannot be determined unambigiously the most likely value is D-S=4=-0.035 meV. For a tetranuclear nickel butterfly, [Ni-4(mu(3)-OH)(2)(O2CCMe3)(6)(EtOH)(6)] 3, three exchange interactions are required, two anti-ferromagnetic and one weakly ferromagnetic; the resulting ground state is S=0. The data enable us to estimate the zero-field splitting of single Ni(II) ions involved in the cage as D-i=+1.0 meV. Both 1 and 2 are therefore expected to be new single molecule magnets.

Original languageEnglish
Pages (from-to)2758-2766
Number of pages9
JournalDalton Transactions
Issue number17
DOIs
Publication statusPublished - 2004

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