| Autor: |
Herder JA; Department of Chemistry, The George Washington University, 800 22nd Street, NW, Washington, District of Columbia 20052, United States., Kruse SJ; Department of Chemistry, University of Iowa, Chemistry Building W374, Iowa City, Iowa 55242, United States., Nicholas AD; Department of Chemistry, The George Washington University, 800 22nd Street, NW, Washington, District of Columbia 20052, United States.; Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States., Forbes TZ; Department of Chemistry, University of Iowa, Chemistry Building W374, Iowa City, Iowa 55242, United States., Walter ED; Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States., Cho H; Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States., Cahill CL; Department of Chemistry, The George Washington University, 800 22nd Street, NW, Washington, District of Columbia 20052, United States. |
| Abstrakt: |
Reported are the syntheses, structural characterizations, and luminescence properties of three novel [UO 2 Cl 4 ] 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 [UO 2 Cl 4 ] 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. |
