In this report, we describe the photoluminescence of a homoleptic uranium(IV) alkoxide complex. Excitation of [Li(THF)]2[UIV(OtBu)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(OtBu)6] and [UVI(OtBu)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.
Valerio, Leyla R., et al. "Photoluminescence of a Uranium(IV) Alkoxide Complex." JACS Au, vol. 5, no. 1, Dec. 2024. https://doi.org/10.1021/jacsau.4c01022
Valerio, Leyla R., Chowdhury, Sabyasachi Roy, Lewis, Rob, Knowles, Kathryn E., Vlaisavljevich, Bess, & Matson, Ellen M. (2024). Photoluminescence of a Uranium(IV) Alkoxide Complex. JACS Au, 5(1). https://doi.org/10.1021/jacsau.4c01022
Valerio, Leyla R., Chowdhury, Sabyasachi Roy, Lewis, Rob, et al., "Photoluminescence of a Uranium(IV) Alkoxide Complex," JACS Au 5, no. 1 (2024), https://doi.org/10.1021/jacsau.4c01022
@article{osti_2507116,
author = {Valerio, Leyla R. and Chowdhury, Sabyasachi Roy and Lewis, Rob and Knowles, Kathryn E. and Vlaisavljevich, Bess and Matson, Ellen M.},
title = {Photoluminescence of a Uranium(IV) Alkoxide Complex},
annote = {In this report, we describe the photoluminescence of a homoleptic uranium(IV) alkoxide complex. Excitation of [Li(THF)]2[UIV(OtBu)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(OtBu)6] and [UVI(OtBu)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.},
doi = {10.1021/jacsau.4c01022},
url = {https://www.osti.gov/biblio/2507116},
journal = {JACS Au},
issn = {ISSN 2691-3704},
number = {1},
volume = {5},
place = {United States},
publisher = {American Chemical Society (ACS)},
year = {2024},
month = {12}}