Pressure‐Induced Encapsulation of Cs+ Cations within an 18‐Crown‐6 Cavity: Insights from X‐ray Diffraction, Raman Spectroscopy, and DFT Calculations
Abstract
This study utilizes single-crystal X-ray diffraction in a diamond anvil cell (DAC) to explore the structural response of [Cs(18-Crown-6)][SbCl6] under high pressure (HP). Notably, the pressure drives large Cs atoms closer to the center of the crown ether cavity, ultimately requiring pressures of 3 GPa for its complete encapsulation. Remarkably, the absence of short contacts in the crystal classifies the material as a "loose crystal" offering a unique model for understanding compression mechanisms. The crystal exhibits highly anisotropic compression behavior with an impressive volume reduction and non-linear pressure - unit-cell parameters relationships facilitated by the absence of short CH center dot center dot center dot Cl contacts up to 0.9 GPa. Beyond this pressure, steric repulsion due to shortening H center dot center dot center dot Cl and H center dot center dot center dot H interactions hinders further effective compression, so pressure dependence on unit cell parameters and volume becomes more linear. The behavior of [Cs(18-Crown-6)][SbCl6] at different conditions was studied using Raman spectroscopy and supplemented by DFT calculations. Show more
Permanent link
https://doi.org/10.3929/ethz-b-000681553Publication status
publishedExternal links
Journal / series
European Journal of Inorganic ChemistryVolume
Pages / Article No.
Publisher
Wiley-VCHSubject
Single crystal X-Ray diffraction; high pressure; 18-Crown-6; Raman spectra; DFT calculationsFunding
212011 - Scholars at Risk Application_Ukraine_Dr. Eduard Rusanov (Dr. Woerle #38; Prof. Kovalenko) (SNF)
216018 - Scholars at Risk Application_Ukraine_Dr. Eduard Rusanov EXTENSION (Dr. Woerle #38; Prof. Kovalenko) (SNF)
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