A family of fourteen soluble stable macrocyclic [NiII3LnIII] heterometallic 3d–4f complexes - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Frontiers Année : 2015

A family of fourteen soluble stable macrocyclic [NiII3LnIII] heterometallic 3d–4f complexes

Résumé

A family of fourteen tetranuclear, 3d–4f heterometallic nickel(II)–lanthanide(III) complexes of the hexa-imine macrocycle (LPr)6−, with general formula NiIILnIII(LPr)(NO ) ·xsolvents (LnIII = LaIII, CeIII, PrIII, NdIII,33 3 SmIII, EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII, YbIII or LuIII), were prepared in a one-pot synthesis using a 3 : 1 : 3 : 3 reaction of nickel(II) acetate, the appropriate lanthanide(III) nitrate, the dialdehyde 1,4-diformyl- 2,3-dihydroxybenzene (H2LAld) and 1,3-diaminopropane. In addition, three tetranuclear heterometallic nickel(II)–lanthanide(III) complexes of H2LAld, with general formula NiIILnIII(LAld) (NO ) ·xsolvents, were 3 3 3 deliberately prepared (LnIII = LaIII, DyIII or YbIII) as in effect they represent intermediates en route to the above macrocyclic complexes. Whilst single crystals of the macrocyclic complexes were not forthcoming, X-ray crystal structure determinations on NiIILnIII(LAld) (NO ) ·xsolvents (LnIII = DyIII or YbIII) confirmed that 3 3 3 3 the large ten-coordinate lanthanide(III) ion is bound in the central O6 pocket while the smaller six-coordi- nate nickel(II) ions are bound in the outer O4 pockets. In all fourteen cases, addition of the diamine to this intermediate (all in one pot) gives the tetrametallic [3 + 3] macrocyclic product. The magnetic properties of all fourteen macrocyclic complexes were measured down to 1.8 K to check for Single-Molecule Magnet behaviour, but no slow dynamics of magnetisation was observed.
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hal-01224099 , version 1 (04-11-2015)

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Humphrey L. C. Feltham, Sébastien Dhers, Mathieu Rouzières, Rodolphe Clérac, Annie K. Powell, et al.. A family of fourteen soluble stable macrocyclic [NiII3LnIII] heterometallic 3d–4f complexes. Inorganic Chemistry Frontiers, 2015, 2, pp. 982-990. ⟨10.1039/c5qi00130g⟩. ⟨hal-01224099⟩

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