Modelling ion-pair geometries and dynamics in a 1-ethyl-1-methylpyrrolidinium-based ion-conductive crystal

Fangfang Chen; Haijin Zhu; Maria Forsyth

doi:10.1002/cphc.201402394

Modelling ion-pair geometries and dynamics in a 1-ethyl-1-methylpyrrolidinium-based ion-conductive crystal

Fangfang Chen^*, Haijin Zhu, Maria Forsyth

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

Full conformational and energy explorations are conducted on an organic ionic plastic crystal, 1-ethyl-1-methylpyrrolidium tetrafluoroborate [C₂mpyr][BF₄]. The onsets of various stages of dynamic behaviour, which appear to account for low-temperature solid-solid phase transitions, are investigated by using quantum-chemical simulations. It is suggested that pseudorotation of the pyrrolidine ring occurs in the first instance; the partial rotation of the entire cation subsequently occurs and may be accompanied by reorientation of the ethyl chain as the temperature increases further. A cation-anion configuration, whereby BF₄^- interacts with the C₂mpy cation from the side of the ring, is the most likely structure in the low-temperature phase IV region. These interpretations are supported by ¹³C nuclear magnetic resonance chemical-shift analysis.

Original language	English
Pages (from-to)	3530-3535
Number of pages	6
Journal	ChemPhysChem
Volume	15
Issue number	16
DOIs	https://doi.org/10.1002/cphc.201402394
State	Published - 3 Nov 2014
Externally published	Yes

Keywords

Density functional calculations
Nmr spectroscopy
Organic ionic plastic crystal
Solid-state electrolyte
Structure and dynamics

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10.1002/cphc.201402394

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title = "Modelling ion-pair geometries and dynamics in a 1-ethyl-1-methylpyrrolidinium-based ion-conductive crystal",

abstract = "Full conformational and energy explorations are conducted on an organic ionic plastic crystal, 1-ethyl-1-methylpyrrolidium tetrafluoroborate [C2mpyr][BF4]. The onsets of various stages of dynamic behaviour, which appear to account for low-temperature solid-solid phase transitions, are investigated by using quantum-chemical simulations. It is suggested that pseudorotation of the pyrrolidine ring occurs in the first instance; the partial rotation of the entire cation subsequently occurs and may be accompanied by reorientation of the ethyl chain as the temperature increases further. A cation-anion configuration, whereby BF4- interacts with the C2mpy cation from the side of the ring, is the most likely structure in the low-temperature phase IV region. These interpretations are supported by 13C nuclear magnetic resonance chemical-shift analysis.",

keywords = "Density functional calculations, Nmr spectroscopy, Organic ionic plastic crystal, Solid-state electrolyte, Structure and dynamics",

author = "Fangfang Chen and Haijin Zhu and Maria Forsyth",

note = "Publisher Copyright: {\textcopyright} 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2014",

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doi = "10.1002/cphc.201402394",

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T1 - Modelling ion-pair geometries and dynamics in a 1-ethyl-1-methylpyrrolidinium-based ion-conductive crystal

AU - Chen, Fangfang

AU - Zhu, Haijin

AU - Forsyth, Maria

PY - 2014/11/3

Y1 - 2014/11/3

N2 - Full conformational and energy explorations are conducted on an organic ionic plastic crystal, 1-ethyl-1-methylpyrrolidium tetrafluoroborate [C2mpyr][BF4]. The onsets of various stages of dynamic behaviour, which appear to account for low-temperature solid-solid phase transitions, are investigated by using quantum-chemical simulations. It is suggested that pseudorotation of the pyrrolidine ring occurs in the first instance; the partial rotation of the entire cation subsequently occurs and may be accompanied by reorientation of the ethyl chain as the temperature increases further. A cation-anion configuration, whereby BF4- interacts with the C2mpy cation from the side of the ring, is the most likely structure in the low-temperature phase IV region. These interpretations are supported by 13C nuclear magnetic resonance chemical-shift analysis.

AB - Full conformational and energy explorations are conducted on an organic ionic plastic crystal, 1-ethyl-1-methylpyrrolidium tetrafluoroborate [C2mpyr][BF4]. The onsets of various stages of dynamic behaviour, which appear to account for low-temperature solid-solid phase transitions, are investigated by using quantum-chemical simulations. It is suggested that pseudorotation of the pyrrolidine ring occurs in the first instance; the partial rotation of the entire cation subsequently occurs and may be accompanied by reorientation of the ethyl chain as the temperature increases further. A cation-anion configuration, whereby BF4- interacts with the C2mpy cation from the side of the ring, is the most likely structure in the low-temperature phase IV region. These interpretations are supported by 13C nuclear magnetic resonance chemical-shift analysis.

KW - Density functional calculations

KW - Nmr spectroscopy

KW - Organic ionic plastic crystal

KW - Solid-state electrolyte

KW - Structure and dynamics

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DO - 10.1002/cphc.201402394

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SN - 1439-4235

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JO - ChemPhysChem

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ER -

Modelling ion-pair geometries and dynamics in a 1-ethyl-1-methylpyrrolidinium-based ion-conductive crystal

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Keywords

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