Journal article
Photoluminescence of a Uranium(IV) Alkoxide Complex
JACS Au, Vol.5(1), pp.332-342
01/27/2025
DOI: 10.1021/jacsau.4c01022
Abstract
In this report, we describe the photoluminescence of a homoleptic uranium(IV) alkoxide complex. Excitation of [Li(THF)]2[UIV(O t Bu)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)][UV(O t Bu)6] and [UVI(O t Bu)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.
Details
- Title: Subtitle
- Photoluminescence of a Uranium(IV) Alkoxide Complex
- Creators
- Leyla R. Valerio - University of RochesterSabyasachi Roy Chowdhury - University of Iowa, ChemistryRob Lewis - University of RochesterKathryn E. Knowles - University of RochesterBess Vlaisavljevich - University of South DakotaEllen M. Matson - University of Rochester
- Resource Type
- Journal article
- Publication Details
- JACS Au, Vol.5(1), pp.332-342
- Publisher
- Amer Chemical Soc
- DOI
- 10.1021/jacsau.4c01022
- eISSN
- 2691-3704
- Number of pages
- 11
- Grant note
- DE-SC0021917 / Basic Energy Sciences; United States Department of Energy (DOE) U.S. Department of Energy, Office of Science, Basic Energy Sciences Heavy-Element Chemistry program; United States Department of Energy (DOE) NSF; National Science Foundation (NSF) OAC-1626516 / U.S. Department of Energy, Office of Science, Basic Energy Sciences, in the Heavy-Element Chemistry program; United States Department of Energy (DOE) DE-SC0025311 / National Science Foundation Graduate Research Fellowship Program; National Science Foundation (NSF)
- Language
- English
- Electronic publication date
- 12/12/2024
- Date published
- 01/27/2025
- Academic Unit
- Chemistry
- Record Identifier
- 9984759889502771
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