Broadening the scope of uranyl photoreactivity: The oxidation of a uranyl complex anion in solid-state materials



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. Kinetic analyses indicate the degree of quenching follows a second-order rate law with a rate constant dependent on viologen substituent. This phenomenon is proposed to involve the formal transfer of one electron from the [UO2Cl4]2- to the viologen species. This proposed mechanism is supported through a series of calculations and computational work including Rehm-Weller analysis, time-dependent density functional theory (TD-DFT), and density of states (DOS). This work constitutes the first study of an oxidized uranyl complex anion which expands the conventional understanding of uranyl photoreactivity.


Supplementary material

Supporting Information
Supporting information and figures
CheckCif of 1
CheckCif report for compound 1
CheckCif of 2
CheckCif report for compound 2
CheckCif of 3
CheckCif report for compound 3
Cif 1
Crystallographic information file of compound 1
Cif 2
Crystallographic information file of compound 2
Cif 3
Crystallographic information file of compound 3