A family of salts of R-(+)-(3)-hydroxyquinuclidinium [QH]+, with SO42−, BPh4−, BF4− and PF6− counter-anions, have been prepared by the metathesis of [QH]Cl and metal salts of the corresponding anions. Solid solutions of formula [QH](PF6)x(BF4)1−x for x = 0.9, 0.8, 0.7 have also been obtained. The crystalline materials have been investigated by a combination of solid-state techniques, including variable temperature XRD, thermal analyses, multinuclear (11B, 13C, 15N, 19F, and 31P) solid-state NMR spectroscopy, variable temperature wideline 19F T1 relaxation measurements, and micro-Raman spectroscopy to investigate their thermal stability and phase transition behaviors. It has been shown that the salts [QH]PF6 and [QH]BF4 undergo an order–disorder solid–solid phase transition to plastic phases, whereas [QH]2SO4·H2O and [QH]BPh4 do not display any plastic phase transition. Doping [QH]BF4 into the [QH]PF6 lattice up to 30% results in the formation of a solid solution that is plastic in an expanded thermal range, thanks to a phenomenon that we describe here for the first time as “reordering frustration”.

Engineering plastic phase transitions via solid solutions: the case of “reordering frustration” in ionic plastic crystals of hydroxyquinuclidinium salts / Ocak, Samet; Birolo, Rebecca; Carì, Gianluca; Bordignon, Simone; Chierotti, Michele R.; Braga, Dario; Gobetto, Roberto; Salzillo, Tommaso; Venuti, Elisabetta; Yaffe, Omer; d'Agostino, Simone. - In: MOLECULAR SYSTEMS DESIGN & ENGINEERING. - ISSN 2058-9689. - ELETTRONICO. - 7:(2022), pp. 950-962. [10.1039/D2ME00040G]

Engineering plastic phase transitions via solid solutions: the case of “reordering frustration” in ionic plastic crystals of hydroxyquinuclidinium salts

Ocak, Samet;Chierotti, Michele R.
;
Braga, Dario;Salzillo, Tommaso
;
Venuti, Elisabetta;d'Agostino, Simone
2022

Abstract

A family of salts of R-(+)-(3)-hydroxyquinuclidinium [QH]+, with SO42−, BPh4−, BF4− and PF6− counter-anions, have been prepared by the metathesis of [QH]Cl and metal salts of the corresponding anions. Solid solutions of formula [QH](PF6)x(BF4)1−x for x = 0.9, 0.8, 0.7 have also been obtained. The crystalline materials have been investigated by a combination of solid-state techniques, including variable temperature XRD, thermal analyses, multinuclear (11B, 13C, 15N, 19F, and 31P) solid-state NMR spectroscopy, variable temperature wideline 19F T1 relaxation measurements, and micro-Raman spectroscopy to investigate their thermal stability and phase transition behaviors. It has been shown that the salts [QH]PF6 and [QH]BF4 undergo an order–disorder solid–solid phase transition to plastic phases, whereas [QH]2SO4·H2O and [QH]BPh4 do not display any plastic phase transition. Doping [QH]BF4 into the [QH]PF6 lattice up to 30% results in the formation of a solid solution that is plastic in an expanded thermal range, thanks to a phenomenon that we describe here for the first time as “reordering frustration”.
2022
Engineering plastic phase transitions via solid solutions: the case of “reordering frustration” in ionic plastic crystals of hydroxyquinuclidinium salts / Ocak, Samet; Birolo, Rebecca; Carì, Gianluca; Bordignon, Simone; Chierotti, Michele R.; Braga, Dario; Gobetto, Roberto; Salzillo, Tommaso; Venuti, Elisabetta; Yaffe, Omer; d'Agostino, Simone. - In: MOLECULAR SYSTEMS DESIGN & ENGINEERING. - ISSN 2058-9689. - ELETTRONICO. - 7:(2022), pp. 950-962. [10.1039/D2ME00040G]
Ocak, Samet; Birolo, Rebecca; Carì, Gianluca; Bordignon, Simone; Chierotti, Michele R.; Braga, Dario; Gobetto, Roberto; Salzillo, Tommaso; Venuti, Elisabetta; Yaffe, Omer; d'Agostino, Simone
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/893385
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