The article reports the synthesis and structural characterization of a series of Ln(C9H9)3 complexes with the cyclononatetraenyl (Cnt, C9H9) ligand (Ln = Y, Gd, Tb, Dy, Ho, Er, Tm). The Yb and Sm complexes were not obtained and the reaction of the potassium salt of the Cnt ligand with trivalent halides salts of the corresponding metals led to the known bis-Cnt sandwich compounds, Ln(C9H9)2. The X-ray diffraction studies on the trivalent complexes show that the Cnt ligand is significantly bent

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... order to accommodate the large size of the ligand while keeping the aromaticity. When the size of the lanthanide ion decreases, the ligand does not switch away but swings over the metal ion in order to maximize the electrostatic interactions. The 1 H NMR and the UV-Visible spectroscopies were recorded as well as the solid-state magnetism. The UV-Visible spectroscopy highlights a remarkable charge-transfer band in the Tm complex while ligand-based transitions are principally observed with all other metal ions. The magnetic behavior of the series agrees with trivalent lanthanides ions and the computations at the CASSCF level confirm the trivalent electronic structure.