Synthesis, characterization, and density functional theory investigation of (CHN)[NpOCl] and Rb[NpOCl(HO)] chain structures.

The actinyl tetrachloro complex [An(V/VI)OCl] tends to form discrete molecular units in both solution and solid state materials, but related aquachloro complexes have been observed as both discrete coordination compounds and 1-D chain topologies. Subtle differences in the inner sphere coordination significantly influence the formation of structural topologies in the actinyl chloride system, but the exact reasoning for these variations has not been delineated. In the current study, we present the synthesis, structural characterization, and vibrational analysis of two 1-D neptunyl(V) chain compounds: (CHN)[NpOCl] (Np-Gua) and Rb[NpOCl(HO)] (Np-Rb). Bonding and non-covalent interactions (NCIs) in the systems were evaluated using periodic Density Functional Theory (DFT) to link these properties to related phases. We observed ∼6.5% and ∼3.9% weakening of NpO bonds in Np-Gua and Np-Rb compared to the reference Cs[NpOCl]. NCI analysis distinguished specific assembly modes, where Np-Gua was connected hydrogen bonding (N-H⋯Cl and N-H⋯O) and Np-Rb contained both cation interactions (Rb⋯O and Rb⋯Cl) and hydrogen bonding (O-H⋯O) networks. Thermodynamically viable formation pathways for both compounds were explored using DFT methodology. The [NpOCl] and [NpOCl(HO)] substructures were identified as precursors to Np-Gua and [NpOCl(HO)] and [NpOCl(HO)] were isolated as the primary building units of Np-Rb. Finally, we utilized DFT to analyze the vibrational modes for Np-Gua and Np-Rb, where we found evidence of the NpO bond weakening within the Np(V) chain structures compared to [NpOCl].