Conformational Dynamics in an Organic Ionic Plastic Crystal

Liyu Jin, Kate M. Nairn, Chris D. Ling, Haijin Zhu, Luke A O'Dell, Jiaye Li, Fangfang Chen, Adriano F. Pavan, Louis A Madsen, Patrick C. Howlett, Douglas R. Macfarlane, Maria Forsyth, Jennifer M. Pringle

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Understanding the short-range molecular motions of organic ionic plastic crystals is critical for the application of these materials as solid-state electrolytes in electrochemical devices such as lithium batteries. However, the theory of short-range-motions was originally developed for simple molecular plastic crystals and does not take account of strong interionic interactions that are present in organic ionic plastic crystals. Here we report a fundamental investigation of the dynamic behavior of an archetypal example triethyl(methyl)phosphonium bis(fluorosulfonyl)amide ([P1222][FSI]) through calorimetry, impedance spectroscopy, synchrotron X-ray diffraction, and solid-state NMR and Raman spectroscopies. For the first time, we show the presence of conformational dynamics in the solid state for the FSI anion. We relate the dynamics to a unique second-order displacive phase transition of [P1222][FSI]. This detailed analysis suggests a new disorder mechanism involving cooperative motion between the cation and FSI anion in the plastic crystal due to strong interionic interactions.

Original languageEnglish
Pages (from-to)5439-5446
Number of pages8
JournalJournal of Physical Chemistry B
Volume121
Issue number21
DOIs
Publication statusPublished - 1 Jun 2017

Cite this

Jin, L., Nairn, K. M., Ling, C. D., Zhu, H., O'Dell, L. A., Li, J., ... Pringle, J. M. (2017). Conformational Dynamics in an Organic Ionic Plastic Crystal. Journal of Physical Chemistry B, 121(21), 5439-5446. https://doi.org/10.1021/acs.jpcb.7b02780
Jin, Liyu ; Nairn, Kate M. ; Ling, Chris D. ; Zhu, Haijin ; O'Dell, Luke A ; Li, Jiaye ; Chen, Fangfang ; Pavan, Adriano F. ; Madsen, Louis A ; Howlett, Patrick C. ; Macfarlane, Douglas R. ; Forsyth, Maria ; Pringle, Jennifer M. / Conformational Dynamics in an Organic Ionic Plastic Crystal. In: Journal of Physical Chemistry B. 2017 ; Vol. 121, No. 21. pp. 5439-5446.
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title = "Conformational Dynamics in an Organic Ionic Plastic Crystal",
abstract = "Understanding the short-range molecular motions of organic ionic plastic crystals is critical for the application of these materials as solid-state electrolytes in electrochemical devices such as lithium batteries. However, the theory of short-range-motions was originally developed for simple molecular plastic crystals and does not take account of strong interionic interactions that are present in organic ionic plastic crystals. Here we report a fundamental investigation of the dynamic behavior of an archetypal example triethyl(methyl)phosphonium bis(fluorosulfonyl)amide ([P1222][FSI]) through calorimetry, impedance spectroscopy, synchrotron X-ray diffraction, and solid-state NMR and Raman spectroscopies. For the first time, we show the presence of conformational dynamics in the solid state for the FSI anion. We relate the dynamics to a unique second-order displacive phase transition of [P1222][FSI]. This detailed analysis suggests a new disorder mechanism involving cooperative motion between the cation and FSI anion in the plastic crystal due to strong interionic interactions.",
author = "Liyu Jin and Nairn, {Kate M.} and Ling, {Chris D.} and Haijin Zhu and O'Dell, {Luke A} and Jiaye Li and Fangfang Chen and Pavan, {Adriano F.} and Madsen, {Louis A} and Howlett, {Patrick C.} and Macfarlane, {Douglas R.} and Maria Forsyth and Pringle, {Jennifer M.}",
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Jin, L, Nairn, KM, Ling, CD, Zhu, H, O'Dell, LA, Li, J, Chen, F, Pavan, AF, Madsen, LA, Howlett, PC, Macfarlane, DR, Forsyth, M & Pringle, JM 2017, 'Conformational Dynamics in an Organic Ionic Plastic Crystal' Journal of Physical Chemistry B, vol. 121, no. 21, pp. 5439-5446. https://doi.org/10.1021/acs.jpcb.7b02780

Conformational Dynamics in an Organic Ionic Plastic Crystal. / Jin, Liyu; Nairn, Kate M.; Ling, Chris D.; Zhu, Haijin; O'Dell, Luke A; Li, Jiaye; Chen, Fangfang; Pavan, Adriano F.; Madsen, Louis A; Howlett, Patrick C.; Macfarlane, Douglas R.; Forsyth, Maria; Pringle, Jennifer M.

In: Journal of Physical Chemistry B, Vol. 121, No. 21, 01.06.2017, p. 5439-5446.

Research output: Contribution to journalArticleResearchpeer-review

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AU - Li, Jiaye

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AU - Forsyth, Maria

AU - Pringle, Jennifer M.

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AB - Understanding the short-range molecular motions of organic ionic plastic crystals is critical for the application of these materials as solid-state electrolytes in electrochemical devices such as lithium batteries. However, the theory of short-range-motions was originally developed for simple molecular plastic crystals and does not take account of strong interionic interactions that are present in organic ionic plastic crystals. Here we report a fundamental investigation of the dynamic behavior of an archetypal example triethyl(methyl)phosphonium bis(fluorosulfonyl)amide ([P1222][FSI]) through calorimetry, impedance spectroscopy, synchrotron X-ray diffraction, and solid-state NMR and Raman spectroscopies. For the first time, we show the presence of conformational dynamics in the solid state for the FSI anion. We relate the dynamics to a unique second-order displacive phase transition of [P1222][FSI]. This detailed analysis suggests a new disorder mechanism involving cooperative motion between the cation and FSI anion in the plastic crystal due to strong interionic interactions.

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Jin L, Nairn KM, Ling CD, Zhu H, O'Dell LA, Li J et al. Conformational Dynamics in an Organic Ionic Plastic Crystal. Journal of Physical Chemistry B. 2017 Jun 1;121(21):5439-5446. https://doi.org/10.1021/acs.jpcb.7b02780