The Solvate Sponge Crystal (DMF)3NaClO4: Thermal Stability and Mechanism of Reversible, Pressure- or Temperature-Controlled Juicing in a Melt- and 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 (DMF)3NaClO4 and (DMF)2NaClO4 (DMF = N-N′-dimethylformamide). External pressure or heating results in reversible expulsion of liquid DMF from (DMF)3NaClO4 to generate (DMF)2NaClO4. 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 ClO4− 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.