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Modelling Ion‐Pair Geometries and Dynamics in a 1‐Ethyl‐1‐methylpyrrolidinium‐Based Ion‐Conductive Crystal
Author(s) -
Chen Fangfang,
Zhu Haijin,
Forsyth Maria
Publication year - 2014
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201402394
Subject(s) - chemistry , ion , tetrafluoroborate , pseudorotation , ionic liquid , ring (chemistry) , ionic bonding , pyrrolidine , plastic crystal , crystallography , phase (matter) , phase transition , crystal (programming language) , computational chemistry , chemical physics , stereochemistry , organic chemistry , thermodynamics , computer science , programming language , catalysis , physics
Full conformational and energy explorations are conducted on an organic ionic plastic crystal, 1‐ethyl‐1‐methylpyrrolidium tetrafluoroborate [C 2 mpyr][BF 4 ]. 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 BF 4 − interacts with the C 2 mpy cation from the side of the ring, is the most likely structure in the low‐temperature phase IV region. These interpretations are supported by 13 C nuclear magnetic resonance chemical‐shift analysis.