Molecular Lanthanide Switches for Magnetism and Photoluminescence

Abstract

AbstractSolvation of [(CNT)Ln(η8‐COT)] (Ln=La, Ce, Nd, Tb, Er; CNT=cyclononatetraenyl, i.e., C9H9−; COT=cyclooctatetraendiid, i.e., C8H82−) complexes with tetrahydrofuran (THF) gives rise to neutral [(η4‐CNT)Ln(thf)2(η8‐COT)] (Ln=La, Ce) and ionic [Ln(thf)x(η8‐COT)][CNT] (x=4 (Ce, Nd, Tb), 3 (Er)) species in a solid‐to‐solid transformation. Due to the severe distortion of the ligand sphere upon solvation, these species act as switchable luminophores and single‐molecule magnets. The desolvation of the coordinated solvents can be triggered by applying a dynamic vacuum, as well as a temperature gradient stimulus. Raman spectroscopic investigations revealed fast and fully reversible solvation and desolvation processes. Moreover, we also show that a Nd:YAG laser can induce the necessary temperature gradient for a self‐sufficient switching process of the Ce(III) analogue in a spatially resolved manner.