Pressure‐Induced Encapsulation of Cs+ Cations within an 18‐Crown‐6 Cavity: Insights from X‐ray Diffraction, Raman Spectroscopy, and DFT Calculations
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2024-07-10
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Journal Article
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yes
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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.
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published
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27 (20)
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Wiley-VCH
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Subject
Single crystal X-Ray diffraction; high pressure; 18-Crown-6; Raman spectra; DFT calculations
Organisational unit
03934 - Kovalenko, Maksym / Kovalenko, Maksym
02024 - Small Molecule Crystallography Center
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Funding
212011 - Scholars at Risk Application_Ukraine_Dr. Eduard Rusanov (Dr. Woerle & Prof. Kovalenko) (SNF)
216018 - Scholars at Risk Application_Ukraine_Dr. Eduard Rusanov EXTENSION(Dr. Woerle & Prof. Kovalenko) (SNF)
216018 - Scholars at Risk Application_Ukraine_Dr. Eduard Rusanov EXTENSION(Dr. Woerle & Prof. Kovalenko) (SNF)