Syntheses and Structures of the First Lanthanide-Thiosulfate Complexes and the Subsequent Formation of Mixed Thiosulfate-Sulfite Compounds

The first rare-earth (RE) thiosulfate complexes, RE(S2O3)(6)(9-), have been crystallized via room-temperature reactions and structurally characterized through single-crystal Xray diffraction. The incorporation of KCl was essential to their successful crystallization. Then through the use of both solvent-layering and heating techniques, these complexes can undergo structural changes through breaking the thiosulfate S-S bond and forming the sulfite anion (SO32-). Using the former approach, two novel lanthanide mixed thiosulfate-sulfite compounds were synthesized; moreover, through the addition of low-temperature heating time, a new structure with a higher proportion of sulfite to thiosulfate was produced. These syntheses and techniques open the door to a new family of unexplored complexes containing hard lanthanide cations and soft thiosulfate anions. The 23 compounds discussed herein show how simple changes to the synthetic process illuminate manipulatable redox reactions able to produce unique rare-earth thiosulfate materials.

Automated summary

This study presents the crystallization and structural characterization of rare-earth thiosulfate complexes, revealing the structural changes and novel compounds that can be synthesized through different techniques. The findings highlight the potential for manipulatable redox reactions in producing unique materials in the unexplored family of rare-earth thiosulfate complexes containing hard lanthanide cations and soft thiosulfate anions.