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Updated: Jun 17, 2026
10:42
Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Structural insights into heavy chalcogen polycations and their stabilization via (hydrogen)polysulfates
Jan Langwald1, Sergi Burguera2, Antonio Frontera2
1Institute of Inorganic and Materials Chemistry, University of Cologne, Greinstr. 6, 50939 Cologne, Germany. mathias.wickleder@uni-koeln.de.
Dalton Transactions (Cambridge, England : 2003)
|June 16, 2026
Summary
New selenium and tellurium cations like [Se4]2+ and [Te4]2+ were stabilized as polysulfates. These novel compounds reveal unique chalcogen bonding interactions and electrophilic properties, advancing inorganic chemistry.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Computational Chemistry
Background:
- Colorful solutions of tellurium cations have been known for over 200 years but lacked solid-state investigation.
- Stabilization of polycationic chalcogens in solid-state matrices is challenging.
- Understanding cation-anion interactions is crucial for designing novel materials.
Purpose of the Study:
- To prepare and characterize novel polysulfate salts of [Se4]2+, [Te4]2+, and [Te6]4+ cations.
- To investigate the solid-state structures and properties of these new chalcogen compounds.
- To elucidate the nature of cation-anion interactions, particularly chalcogen bonding, using computational methods.
Main Methods:
- Synthesis and characterization of polysulfate salts using chlorosulfuric acid/sulfur trioxide media.
- X-ray crystallography for solid-state structure determination.
- Density Functional Theory (DFT) calculations, including MEP surface plots, QTAIM, and NBO analyses.
Main Results:
- Successful preparation and characterization of [Se4][S2O7], [Se4][HS2O7]2, [Se4][HS3O10]2, [Te4][HS3O10]2, [Te6][HS3O10]4, and [Te6][S4O13]2.
- Identification of diverse chalcogen bonding (ChB) modes, including bifurcated and standard σ-hole interactions.
- Demonstration of the [Se4]2+ dication's electrophilic duality and the role of auxiliary Ch⋯O contacts in stabilizing polycationic chalcogens.
Conclusions:
- This study reports the first stabilization and solid-state investigation of tellurium cations synthesized from chlorosulfuric acid/sulfur trioxide media.
- Novel cation-anion interactions, specifically various modes of chalcogen bonding, were characterized in detail.
- The findings enhance the understanding of polycationic chalcogen stabilization and their unique electronic properties.
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