Single molecule magnetic behaviour in lanthanide naphthalenesulfonate complexes

The use of 2-naphthalenesulfonate (NAS) ligand in lanthanide chemistry afforded a family of isostructural mononuclear lanthanide complexes with formula [Ln(NAS)2(H2O)6](NAS)·3H2O [Ln = Tb (1), Dy (2), Er (3), Yb (4)]. Crystallographic studies determine a square antiprismatic geometry (D4d) for the Ln centre and crystallization in unprecedented chiral space group. The latter was further confirmed by the observation of Cotton effects in single crystal circular dichroism (CD) spectra. Static and dynamic magnetic measurements identify weak intermolecular dipolar interactions in 2, and such effects can be waived by dilution, which was noted by the detection of zero-field single molecule magnet (SMM) behaviour and hysteresis loop in the magnetically diluted sample (5). Compounds 2-4 exhibit SMM behaviours with energy barriers of 53, 32 and 45 K, respectively. To the best of our knowledge, these complexes provide the first examples of pure 4f sulfonate-based SMMs