Plutonium chlorido nitrato complexes: ligand competition and computational metrics for assembly and bonding

Four new [Pu(iv)Cln(NO3)6-n]2- (n = 0, 2, 3) and [Pu(vi)O2Cl3(NO3)]2- containing materials were crystallized from acidic, aqueous media and structurally characterized. The anions are assembled via hydrogen and halogen bonding motifs, which are rationalized computationally. The Pu-NO3 and -Cl bonds were probed using QTAIM and NLMO analyses and found to be polar and largely ionic.