Spectroscopic speciation and structural characterisation of uranyl(VI) interaction with pyridine carboxylic acid N-oxide derivatives

Spectroscopic speciation of U(VI) solutions holding pyridine carboxylic acid N-oxides in a range pH 2.3–4.5 results in the single component spectrum of the U(VI) isonicotinic acid N-oxide complex. The molar absorption is 14 ± 2 L mol−1 cm−1 at 415.4 nm. The formation constant lg KUL = 2.1 ± 0.2 (k = 2) is derived from solution modelling and by multivariate chemometric analysis. The first crystal structure analysis of a U(VI) pyridine carboxylic acid N-oxide revealed a sheet-like structure where the isonicotinic acid N-oxide binds to the uranyl(VI) both bidentately by the carboxylate group and monodentately by the N–O group. The single component spectrum of the [UO2L]+ (where L− is isonicotinate N-oxide) is compared to the small number of other U(VI) single ligand species. The comparison revealed the possible pitfalls of U(VI) spectroscopic speciation close to the pH region where U(VI) hydrolysis starts to interfere. On basis of the results for U(VI)–L coordination and physicochemical properties of the pyridine carboxylic acid N-oxides some conclusions could be drawn on the likely behaviour of nicotinic acid N-oxide and picolinic acid N-oxide. For the former, complex formation in a narrow range of pH and U(VI) concentrations close to the hydrolysis range of U(VI) might reveal thermodynamic data. In the case of picolinic acid N-oxide, additional experimental evidence is required to characterize suitable conditions.

Graphical abstractSpectroscopic speciation of uranyl with pyridine carboxylic acid N-oxides in solution has been studied. The formation constant of the U(VI) isonicotinic acid N-oxide complex as lg KUL = 2.1 ± 0.2 was derived from solution modelling and by multivariate chemometric analysis. Crystal data analysis of U(VI)/isonicotinic acid N-oxide revealed a sheet-like structure.Figure optionsDownload full-size imageDownload as PowerPoint slide