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Rare-earth element separation processes often rely on a small decrease in ionic radii along the series of elements. Separation processes based on the distinct optical properties of REs remain less explored, although photochemical methods may offer a viable alternative. Accurate selection of the synthetic precursors of a photoswitchable acylhydrazonic ligand led to a system that could quantitatively isomerize (E−to−Z) upon irradiation with commercial LED lights. Coordination of the photoswitch with RE^III nitrates (RE = La−Lu except Pm and Y) resulted in the retention of the photoswitching properties observed in solution. The lower binding affinity of the generated Z−isomer with RE^IIImore » ions yielded the dissociation of the complexes upon irradiation (photodissociation) with the release of RE−nitrates in solution. The rate of the reaction was found to be dependent on the optical properties of the RE^III ions, with nonemissive complexes (no 4f excited states) dissociating faster than emissive ones (having accessible 4f excited states). A thorough solid-state characterization of the complexes was performed by using crystallographic and photochemical methods. Ultimately, the accessibility of the 4f excited states of the metals following light irradiation and excitation of the ligand led to a decrease in the rate of the reaction due to quenching of the ligand excited state. These results demonstrate that the direct modulation of the metal coordination environment, combined with the metal-dependent reaction rate, could provide a strategy for the development of RE−separation processes based on differences in their optical properties.« less

Facilitating different chemistries between the rare earth (RE = La–Lu, Sc, Y) ions is of significant interest for their separations. While the bulk of attention has been on maximizing the small differences in their ground state chemistry, interest is beginning to shift toward the differences in their electronic excited states. In this work, we demonstrate modulation of the photostationary state of an azobenzene derivative, Na1, via chelation to a series of RE^IIIDO3A (DO3A = 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) complexes. The extent of photoisomerization of 1^– follows the trend in REIII Lewis acidity with two exceptions: Sm^III and Er^III. UV–vis spectroscopy, titration experiments,more » and computational analysis show that these exceptions are a result of energy transfer rather than differences in ground state chemistry. Finally, these results open a pathway to differentiate REs by new photochemical means.« less