Photoluminescence of a Uranium(IV) Alkoxide Complex

Valerio, Leyla R.; Chowdhury, Sabyasachi Roy; Lewis, Rob; Knowles, Kathryn E.; Vlaisavljevich, Bess; Matson, Ellen M.

doi:10.1021/jacsau.4c01022

Title: Photoluminescence of a Uranium(IV) Alkoxide Complex

Journal Article · 12 December 2024 · JACS Au

DOI: https://doi.org/10.1021/jacsau.4c01022 · OSTI ID:2507116

Valerio, Leyla R. ^[1];

^[2]; Lewis, Rob ^[1];

^[1];

^[2];

^[1]

University of Rochester, NY (United States)
University of South Dakota, Vermillion, SD (United States); University of Iowa, Iowa City, IA (United States)

In this report, we describe the photoluminescence of a homoleptic uranium(IV) alkoxide complex. Excitation of [Li(THF)]₂[U^IV(O^tBu)₆] leads to the first example of photoluminescence from a well-defined actinide complex originating from an f–f excitation, supported by second order multiconfigurational electronic structure calculations including spin–orbit coupling. These calculations show strong spin–orbit coupling between the excited triplet and singlet states for the 5f-orbital manifold, which leads to a long-lived excited state lifetime of 0.85 s at low temperature. The photophysical properties of homoleptic uranium(V) and uranium(VI) tertbutoxide complexes are also presented; we find that oxidation of the uranium(IV) alkoxide results in quenching of luminescence in [Li(THF)][U^V(O^tBu)₆] and [U^VI(O^tBu)₆]. This is attributed to competing ligand to metal charge transfer absorption processes shifted to lower energy upon oxidation of the actinide center, which mask the relevant f–f transitions in the visible region of the electronic absorption spectrum.

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Research Organization:: Univ. of Rochester, NY (United States); University of Iowa, Iowa City, IA (United States); University of Rochester, NY (United States); University of South Dakota, Vermillion, SD (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0020436; SC0021917; SC0023022; SC0025311

OSTI ID:: 2507116

Journal Information:: JACS Au, Journal Name: JACS Au Journal Issue: 1 Vol. 5; ISSN 2691-3704

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
CASSCF/CASPT2 calculations
absorption
actinides
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excited states
f–f excitation
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ligand
ligands
photoluminescence
uranium

Title: Photoluminescence of a Uranium(IV) Alkoxide Complex

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