Breaking a Lewis Acidity Trend for Rare Earths by Excited State Quenching

Wilharm, Randall K.; Gau, Michael R.; Trauner, Dirk; Schelter, Eric J.

doi:10.1021/jacs.5c05257

Title: Breaking a Lewis Acidity Trend for Rare Earths by Excited State Quenching

Journal Article · Thu Jul 24 00:00:00 UTC 2025 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.5c05257 · OSTI ID:2997475

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Univ. of Pennsylvania, Philadelphia, PA (United States)

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, 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.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0017259

OSTI ID:: 2997475

Report Number(s):: DOE-UPENN--17259-2

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 31 Vol. 147; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
absorption
cations
energy transfer
excited states
photoisomerization
photoswitches
rare earths
separations

Title: Breaking a Lewis Acidity Trend for Rare Earths by Excited State Quenching

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