Stability, speciation and spectral properties of NpO₂⁺ complexes with pyridine monocarboxylates in aqueous solution

Neptunyl ion as NpO₂⁺ is the least reacting and most mobile radioactive species among all the actinides. The picolinic acid used for decontamination is co-disposed along with the radioactive waste. Thus, in long term storage of HLW, there is high possibility of interaction of actinides and long lived fission products with the picolinate and can cause migration. The complexation of NpO₂⁺ with the three structural isomers of pyridine monocarboxylates provides an insight to explore the role of hetero atom (nitrogen) with respect to key binding moiety (carboxylate). In the present study, the log β values, speciation and spectral properties of NpO₂⁺ complexes with pyridine monocarboxylates viz. picolinate, nicotinate and isonicotinate, have been studied at 298K in 0.1M NaClO₄ medium using spectrophotometry. The complexation reactions involving protonated ligands are always accompanied by protonation/deprotonation process; thus, the protonation constants of all the three pyridine monocarboxylates under same conditions were also determined by potentiometry. The spectrophotometric data analysis for complexation of NpO₂⁺ with pyridine monocarboxylates indicated the presence of ML and ML₂ complexes with log β values of 2.96±0.04, 5.67±0.08 for picolinate, 1.34±0.09, 1.65±0.12 for nicotinate and 1.52±0.04, 2.39±0.06 for isonicotinate. The higher values of log β for picolinate were attributed to chelation while in other two isomers, the binding is through carboxylate group only. Density Functional Theory (DFT) calculations were carried out to get optimized geometries and electrostatic charges on various atoms of the complexes and free pyridine monocarboxylates to support the experimental data. The higher stability of NpO₂⁺ nicotinate and isonicotinate complexes compared to simple carboxylates and the difference in log β between the two is due to the charge polarization from unbound nitrogen to the bound carboxylate oxygen atoms.