A family of fourteen soluble stable macrocyclic [Ni(3)(II)Ln(III)] heterometallic 3d-4f complexes

作者：Feltham Humphrey L C; Dhers Sebastien; Rouzieres Mathieu; Clerac Rodolphe; Powell Annie K; Brooker Sally

来源：Inorganic Chemistry Frontiers, 2015, 2(11): 982-990.

DOI：10.1039/c5qi00130g

A family of fourteen tetranuclear, 3d-4f heterometallic nickel(II)-lanthanide(III) complexes of the hexaimine macrocycle (L-Pr)(6-), with general formula Ni(3)(II)Ln(III)(L-Pr)(NO3)(3)center dot xsolvents (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 (H2LAld) and 1,3-diaminopropane. In addition, three tetranuclear heterometallic nickel(II)-lanthanide(III) complexes of H2LAld, with general formula Ni(3)(II)Ln(III)(L-Ald)(3)(NO3)(3)center dot xsolvents, 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 Ni(3)(II)Ln(III)(L-Ald)(3)(NO3)(3)center dot xsolvents (Ln(III) = Dy-III or Yb-III) confirmed that the large ten-coordinate lanthanide(III) ion is bound in the central O-6 pocket while the smaller six-coordinate nickel(II) ions are bound in the outer O-4 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.

• 出版日期2015