Molecules, Vol. 27, Pages 147: Synthesis, Crystal Structures, and Spectroscopic Properties of Novel Gadolinium and Erbium Triphenylsiloxide Coordination Entities
Molecules doi: 10.3390/molecules27010147
In alkali metal and lanthanide coordination chemistry, triphenylsiloxides seem to be unduly underappreciated ligands. This is as surprising as that such substituents play a crucial role, among others, in stabilizing rare oxidation states of lanthanide ions, taking a part of intramolecular and molecular interactions stabilizing metal-oxygen cores and many others. This paper reports the synthesis and characterization of new lithium [Li4(OSiPh3)4(THF)2] (1), and sodium [Na4(OSiPh3)4] (2) species, which were later used in obtaining novel gadolinium [Gd(OSiPh3)3(THF)3]&middot;THF (3), and erbium [Er(OSiPh3)3(THF)3]&middot;THF (4) triphenylsiloxides. Crystal structures were determined for all 1&ndash;4 compounds, and in addition, IR, Raman, absorption spectroscopy studies were conducted for 3 and 4 lanthanide compounds. Furthermore, direct current (dc) variable-temperature magnetic susceptibility measurements on polycrystalline samples of 3 and 4 were carried out in the temperature range 1.8&ndash;300 K. The 3 shows behavior characteristics for the paramagnetism of the Gd3+ ion. In contrast, the magnetic properties of 4 are dominated by the crystal field effect on the Er3+ ion, masking the magnetic interaction between magnetic centers of neighboring molecules.
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