Telluronium Cation Coordination of Crown Ethers and Polyethers through Chalcogen Bonding: Coulombically…

Abstract

The ability of the telluronium cation [Ar3Te]+ to bind crown ethers and acyclic polyethers through chalcogen bonding is investigated in both the solid state and in solution. Several 1:1 molecular complexes with polyoxygenated ligands of varying size and functionality were crystallized and analyzed by X-ray diffraction, revealing short Te•••O interactions (dTe-O below the sum of van der Waals radii) and high linearity (Ar-Te-O angles in the range 163-178°). NMR and DOSY (Diffusion Ordered NMR Spectroscopy) experiments confirm that these interactions persist in solution. Isothermal Titration Calorimetry provides the thermodynamic parameters for the telluronium–crown ether and telluronium–polyether equilibria, with association constants reaching Ka ~ 106 for the 5- to 7-membered crown ethers. Based on these results, the templating effect of the telluronium cation on acyclic polyethers is further demonstrated by its ability to promote the ring-closure of a long polyether bearing both bromo and hydroxy termini. Theoretical analysis of the ligand-Te interaction points to a dominant Coulombic contribution, supported by dispersion forces, in stabilizing polyether binding to the Te center. Although the minor covalent contribution operates a crucial anchoring role, it is not sufficient to restrict the O atoms to exclusive -hole interactions, suggesting a fluxional dynamic behavior in solution in which all O atoms dynamically interact with the Te center.

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BibTeX

@misc{groslambert2026telluronium,
  title = {{Telluronium Cation Coordination of Crown Ethers and Polyethers through Chalcogen Bonding: Coulombically Driven Strong Association and Templated Cyclization}},
  author = {Loïc Groslambert and Andres Padilla-Hernandez and Yann Cornaton and Patrick Pale and Jean-Pierre P Djukic and Victor Mamane},
  howpublished = {HAL},
  year = {2026},
  month = jul,
  doi = {10.26434/chemrxiv.15006689/v1},
  url = {https://hal.science/hal-05797304v1},
  note = {CC BY-NC 4.0},
}

RIS

TY  - UNPB
TI  - Telluronium Cation Coordination of Crown Ethers and Polyethers through Chalcogen Bonding: Coulombically Driven Strong Association and Templated Cyclization
AU  - Loïc Groslambert
AU  - Andres Padilla-Hernandez
AU  - Yann Cornaton
AU  - Patrick Pale
AU  - Jean-Pierre P Djukic
AU  - Victor Mamane
PY  - 2026
DA  - 2026/07/29
PB  - HAL
DO  - 10.26434/chemrxiv.15006689/v1
UR  - https://hal.science/hal-05797304v1
AB  - The ability of the telluronium cation [Ar3Te]+ to bind crown ethers and acyclic polyethers through chalcogen bonding is investigated in both the solid state and in solution. Several 1:1 molecular complexes with polyoxygenated ligands of varying size and functionality were crystallized and analyzed by X-ray diffraction, revealing short Te•••O interactions (dTe-O below the sum of van der Waals radii) and high linearity (Ar-Te-O angles in the range 163-178°). NMR and DOSY (Diffusion Ordered NMR Spectroscopy) experiments confirm that these interactions persist in solution. Isothermal Titration Calorimetry provides the thermodynamic parameters for the telluronium–crown ether and telluronium–polyether equilibria, with association constants reaching Ka ~ 106 for the 5- to 7-membered crown ethers. Based on these results, the templating effect of the telluronium cation on acyclic polyethers is further demonstrated by its ability to promote the ring-closure of a long polyether bearing both bromo and hydroxy termini. Theoretical analysis of the ligand-Te interaction points to a dominant Coulombic contribution, supported by dispersion forces, in stabilizing polyether binding to the Te center. Although the minor covalent contribution operates a crucial anchoring role, it is not sufficient to restrict the O atoms to exclusive -hole interactions, suggesting a fluxional dynamic behavior in solution in which all O atoms dynamically interact with the Te center.
ER  -

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