Systematic Study of Solid-State U(VI) Photoreactivity: Long-Lived Radicalization and Electron Transfer in Uranyl Tetrachloride

Jordan A Herder; Samantha J Kruse; Aaron D Nicholas; Tori Z Forbes; Eric D Walter; Herman Cho; Christopher L Cahill

doi:10.1021/acs.inorgchem.3c04144

Back

Systematic Study of Solid-State U(VI) Photoreactivity: Long-Lived Radicalization and Electron Transfer in Uranyl Tetrachloride

Journal article

Peer reviewed

Systematic Study of Solid-State U(VI) Photoreactivity: Long-Lived Radicalization and Electron Transfer in Uranyl Tetrachloride

Jordan A Herder, Samantha J Kruse, Aaron D Nicholas, Tori Z Forbes, Eric D Walter, Herman Cho and Christopher L Cahill

Inorganic chemistry, Vol.63(11), pp.4957-4971

03/18/2024

DOI: 10.1021/acs.inorgchem.3c04144

PMID: 38437845

Files and links (1)

url

https://www.osti.gov/biblio/2377132View

Open Access

Abstract

Reported are the syntheses, structural characterizations, and luminescence properties of three novel [UO2Cl4]2– bearing compounds containing substituted 1,1′-dialkyl-4,4′-bipyridinum dications (i.e., viologens). These compounds undergo photoinduced luminescence quenching upon exposure to UV radiation. This reactivity is concurrent with two phenomena: radicalization of the uranyl tetrachloride anion and photoelectron transfer to the viologen which constitutes the formal transfer of one electron from [UO2Cl4]2– to the viologen species. This behavior is elucidated using electron paramagnetic resonance (EPR) spectroscopy and further probed through a series of characterization and computational techniques including Rehm–Weller analysis, time-dependent density functional theory (TD-DFT), and density of states (DOS). This work provides a systematic study of the photoreactivity of the uranyl unit in the solid state, an under-described aspect of fundamental uranyl chemistry.

Details

Title: Subtitle: Systematic Study of Solid-State U(VI) Photoreactivity: Long-Lived Radicalization and Electron Transfer in Uranyl Tetrachloride
Creators: Jordan A Herder - George Washington University
Samantha J Kruse - University of Iowa
Aaron D Nicholas - George Washington University
Tori Z Forbes - University of Iowa
Eric D Walter - Pacific Northwest National Laboratory
Herman Cho - Pacific Northwest National Laboratory
Christopher L Cahill - George Washington University
Resource Type: Journal article
Publication Details: Inorganic chemistry, Vol.63(11), pp.4957-4971
DOI: 10.1021/acs.inorgchem.3c04144
PMID: 38437845
NLM abbreviation: Inorg Chem
eISSN: 1520-510X
Grant note: DOI: 10.13039/100013145, name: Chemical Sciences, Geosciences, and Biosciences Division, award: DE-FG02-05ER15736
Language: English
Electronic publication date: 03/04/2024
Date published: 03/18/2024
Academic Unit: Civil and Environmental Engineering; Core Research Facilities; Chemistry
Record Identifier: 9984567869802771

Metrics

4 Record Views

2 Times Cited - Web of Science