Conductivity, NMR and crystallographic study of N,N,N,N-tetramethylammonium dicyanamide plastic crystal phases : an archetypal ambient temperature plastic electrolyte material

Seeber, Aaron J., Forsyth, Maria, Forsyth, Craig M., Forsyth, Stewart A., Annat, Gary and MacFarlane, Douglas R. 2003, Conductivity, NMR and crystallographic study of N,N,N,N-tetramethylammonium dicyanamide plastic crystal phases : an archetypal ambient temperature plastic electrolyte material, Physical chemistry chemical physics, vol. 5, no. 12, pp. 2692-2698.

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Title Conductivity, NMR and crystallographic study of N,N,N,N-tetramethylammonium dicyanamide plastic crystal phases : an archetypal ambient temperature plastic electrolyte material
Formatted title Conductivity, NMR and crystallographic study of N,N,N,N-tetramethylammonium dicyanamide plastic crystal phases : an archetypal ambient temperature plastic electrolyte material
Author(s) Seeber, Aaron J.
Forsyth, Maria
Forsyth, Craig M.
Forsyth, Stewart A.
Annat, Gary
MacFarlane, Douglas R.
Journal name Physical chemistry chemical physics
Volume number 5
Issue number 12
Start page 2692
End page 2698
Publisher Royal Society of Chemistry
Place of publication Cambridge, England
Publication date 2003
ISSN 1463-9076
1463-9084
Summary N,N,N,N-Tetramethylammonium dicyanamide (Me4NDCA) has been examined via differential scanning calorimetry (DSC), thermogravimetric analysis, conductivity, single crystal X-ray diffraction and 1H nuclear magnetic resonance (NMR) analyses, and was found to be highly conductive in the solid state (σ =10−3 S cm−2 at 420 K) and to also exhibit unusual plastic crystal behaviour. To investigate the correlation between such behaviour and the occurrence of molecular rotations in the crystal, 1H NMR second moment measurements are compared with calculated values predicted from the crystal structure. While DSC analysis indicates a number of solid–solid transitions at ambient temperatures, subsequent 1H NMR analysis of the Me4N+ cation shows that a variety of rotational motions become active at low (<240 K) temperatures, and that such transitions in rotational states occur over a range of temperatures rather than in a sharp transition. Conductivity analysis reveals that between 320 K and 420 K the conductivity increases by more than six orders of magnitude in the solid state, in line with the transition of the Me4N+ cation to a diffusive state, and that other phase transitions observed in this temperature range have no marked effect on the conductivity. Conduction in this solid state is therefore envisaged to involve a vacancy-diffusion model, involving Me4N+ cation vacancies.
Language eng
Field of Research 039999 Chemical Sciences not elsewhere classified
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1.1 Refereed article in a scholarly journal
Copyright notice ©2003, Owner Societies
Persistent URL http://hdl.handle.net/10536/DRO/DU:30030252

Document type: Journal Article
Collection: Institute for Technology Research and Innovation
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