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Solvate sponge crystals of (DMF)(3)NaClO(4): reversible pressure/temperature controlled juicing in a melt/press-castable sodium-ion conductor

A new type of crystalline solid, termed “solvate sponge crystal”, is presented, and the chemical basis of its properties are explained for a melt- and press-castable solid sodium ion conductor. X-ray crystallography and atomistic simulations reveal details of atomic interactions and clustering in (D...

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Detalles Bibliográficos
Autores principales: Prakash, Prabhat, Ardhra, Shylendran, Fall, Birane, Zdilla, Michael J., Wunder, Stephanie L., Venkatnathan, Arun
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179650/
https://www.ncbi.nlm.nih.gov/pubmed/34168793
http://dx.doi.org/10.1039/d0sc06455f
Descripción
Sumario:A new type of crystalline solid, termed “solvate sponge crystal”, is presented, and the chemical basis of its properties are explained for a melt- and press-castable solid sodium ion conductor. X-ray crystallography and atomistic simulations reveal details of atomic interactions and clustering in (DMF)(3)NaClO(4) and (DMF)(2)NaClO(4) (DMF = N-N′-dimethylformamide). External pressure or heating results in reversible expulsion of liquid DMF from (DMF)(3)NaClO(4) to generate (DMF)(2)NaClO(4). The process reverses upon the release of pressure or cooling. Simulations reveal the mechanism of crystal “juicing,” as well as melting. In particular, cation–solvent clusters form a chain of octahedrally coordinated Na(+)–DMF networks, which have perchlorate ions present in a separate sublattice space in 3 : 1 stoichiometry. Upon heating and/or pressing, the Na(+)⋯DMF chains break and the replacement of a DMF molecule with a ClO(4)(−) anion per Na(+) ion leads to the conversion of the 3 : 1 stoichiometry to a 2 : 1 stoichiometry. The simulations reveal the anisotropic nature of pressure induced stoichiometric conversion. The results provide molecular level understanding of a solvate sponge crystal with novel and desirable physical castability properties for device fabrication.