Seven-coordinate Ln^III complexes assembled from a bulky acacH ligand: their synthesis, structure, photoluminescence...

The reaction of a bulky acetyl acetone ligand 1,3-dimesitylpropane-1,3-dione (MesacacH) with hydrated lanthanide chlorides in the presence of tetramethylammonium hydroxide afforded a new family of neutral mononuclear LnIII complexes [Ln(Mesacac)3(DMF)] (Ln = Dy (1); Tb (2); Y0.91Dy0.09 (3); and Er (4)). The molecular structures of these complexes were confirmed by single crystal X-ray diffraction studies. The coordination geometries of the LnIII centre were analysed by SHAPE analysis which revealed a capped octahedral geometry in 1-4. Photoluminescence studies showed ligand-sensitized green emissions for 2 with an appreciable quantum yield of 0.83%. Static (dc) and dynamic (ac) magnetic studies of complexes 1 and 3 were performed. The dynamic magnetic study revealed that complex 1 exhibits zero-field slow relaxation of the magnetization without showing a clear maximum in the out-of-phase ac susceptibility plots. However, magnetic dilution of 1 with the YIII metal ion (complex 3) and/or the application of a dc magnetic field induces a strong frequency dependence of the ac susceptibility signals with χ''M peaks in the 3-10 K temperature range, thus supporting field-induced SMM behaviour of 1. The relaxation process takes place through a combination of the Orbach and Raman mechanisms. The fitting of the temperature dependence of the relaxation time to the equation τ-1 = τ0-1 exp(-Ueff/kBT) + BTn, allows the extraction of the effective energy barrier Ueff/kB = 70 K (48.7 cm-1) and pre-exponential parameter of τ0 = 2.7 × 10-7 s for the Orbach mechanism (first term) and the parameters B = 0.04 s-1 K-n and n = 6.11, for the Raman mechanism (second term).