Metal-Dependent Photodissociation of Hydrazone Photoswitches from Rare-Earth Complexes

Melegari, Matteo; Wilharm, Randall K.; Silva, Rodolpho Nesta; Artizzu, Flavia; Serpe, Angela; Trauner, Dirk H.; Tegoni, Matteo; Schelter, Eric J.; Marchiò, Luciano

doi:10.1021/jacs.6c03443

Title: Metal-Dependent Photodissociation of Hydrazone Photoswitches from Rare-Earth Complexes

Journal Article · Thu Apr 09 00:00:00 UTC 2026 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.6c03443 · OSTI ID:3366488

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University of Parma (Italy)
University of Pennsylvania, Philadelphia, PA (United States)
University of Eastern Piedmont “A. Avogadro”, Vercelli (Italy)
University of Cagliari (Italy); Environmental Geology and Geoengineering Institute of the National Research Council (IGAG−CNR), Cagliari (Italy)

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^III 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.

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Research Organization:: University of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Organization:: Ministry University and Research, Research Projects of Relevant National Interest Program (MUR PRIN); National Institutes of Health (NIH); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0017259

OSTI ID:: 3366488

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 15 Vol. 148; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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