Novel compounds of a relatively understudied class of materials, uranyl viologens, have been investigated for structural assembly and spectroscopic properties. Despite the extensive research on transition metal-based viologens, few actinide viologen structures are reported. An opportunity therefore exists to study the structural diversity and rich photochemistry surrounding both the uranyl unit and charged viologen species in the solid state. Of particular interest is the possibility of formal electron transfer between inorganic anion and organic cation pairs. To synthesize these compounds, the uranyl species and 4,4’-bipyridine derived viologen chloride salts were combined and allowed to recrystallize via slow evaporation. Single crystal X-ray analysis reveals supramolecular assembly of isolated anionic [UO2Cl4]2- charge balanced by viologen cations. Interactions between the -yl oxygen and the positively charged nitrogen of the viologen are observed by short UO--N atom contacts. Raman spectroscopy was used to probe this interaction and how it influences the nature of the U=O bond. Corresponding photophysical measurements show dominant uranyl absorption and emission profiles in the presence of viologen. The failure to observe viologen features in the photophysical spectra hint at charge transfer between ionic pairs. This presentation will include an overview of uranyl viologen structural features along with spectroscopic responses thereof.

Novel uranyl-viologen compounds: Supramolecular assembly and spectroscopic properties

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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