A family of fourteen soluble stable macrocyclic [NiII3LnIII] heterometallic 3d–4f complexes. Issue 11 (16th September 2015)

• Record Type: Journal Article
• Authors: Feltham, Humphrey L. C.; Dhers, Sébastien; Rouzières, Mathieu; Clérac, Rodolphe; Powell, Annie K.; Brooker, Sally
• Is Part Of: Inorganic chemistry frontiers. Volume 2:Issue 11(2015)
• Page Start: 982
• Page End: 990
• Publication Date: 2015-09-16
• Subjects: Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5qi00130g
• Languages: English
• ISSNs: 2052-1553

Abstract

Abstract : Fourteen macrocyclic NiII3Ln III (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu) complexes were made, and checked for Single-Molecule Magnet behaviour; two acyclic analogues were structurally characterised. Abstract : A family of fourteen tetranuclear, 3d–4f heterometallic nickel(ii )–lanthanide(iii ) complexes of the hexaimine macrocycle (L Pr ) 6−, with general formula NiII3Ln III (L Pr )(NO3 )3 · x solvents (Ln III = La III, Ce III, Pr III, Nd III, Sm III, Eu III, Gd III, Tb III, Dy III, Ho III, Er III, Tm III, Yb III or Lu III ), 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 (H2 L Ald ) and 1, 3-diaminopropane. In addition, three tetranuclear heterometallic nickel(ii )–lanthanide(iii ) complexes of H2 L Ald, with general formula NiII3Ln III (L Ald )3 (NO3 )3 · x solvents, were deliberately prepared (Ln III = La III, Dy III or Yb III ) 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 NiII3Ln III (L Ald )3 (NO3 )3 · x solvents (Ln III = Dy III or Yb III ) confirmed that the large ten-coordinate lanthanide(iii ) ion is bound in the central O6 pocket while the smaller six-coordinate 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.