From lanthanide chlorides to lanthanide pentafluorophenolates via lanthanide N,N-dialkylcarbamates

Neodymium and terbium pentafluorophenolates, containing 1,10-phenanthroline as ancillary ligand, [Ln(OC6F5)3(phen)3], (1 Ln = Nd, 2 Ln = Tb) have been synthesized by reacting the N,N-dibutylcarbamato complexes, [Ln(O2CNBu2)3], easily obtained from aqueous solutions of lanthanide salts, with C6F5OH in the presence of 1,10-phenanthroline. The formation of the sparingly soluble hydrated compound [Tb(OC6F5)3(phen)2(H2O)phen], 3, was observed, due to fortuitous presence of water. Single crystal X-ray diffraction studies on compounds 1, 3 and 3DME (DME = dimethoxyethane) showed coordination numbers (CN) 9 for neodymium in 1 and 8 for terbium in 3 and 3DME, where only two 1,10-phenanthroline ligands are coordinated to terbium, the third forming two hydrogen bonds with the coordinated water. The structural characterisation of [NH2Bu2][C6F5O], 4, showed the organisation of the product in ionic quartets. The photoluminescence spectra of 1 and 2 displayed the typical emissions related to the lanthanide centre in the NIR and visible region, respectively.