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NMR Spectroscopy of Synthetic Metals: Intercalated Graphite

Published online by Cambridge University Press:  15 February 2011

H. A. Resing
Affiliation:
Naval Research Laboratory, Washington, D. C. 20375, and Dept. of Chemistry, The University of Maryland, College Park, MD 20742, USA
M. J. Moran
Affiliation:
Naval Research Laboratory, Washington, D. C. 20375, and Dept. of Chemistry, The University of Maryland, College Park, MD 20742, USA
Gerald Ray Miller
Affiliation:
Naval Research Laboratory, Washington, D. C. 20375, and Dept. of Chemistry, The University of Maryland, College Park, MD 20742, USA
L. G. Banks
Affiliation:
Naval Research Laboratory, Washington, D. C. 20375, and Dept. of Chemistry, The University of Maryland, College Park, MD 20742, USA
C. F. Poranski Jr
Affiliation:
Naval Research Laboratory, Washington, D. C. 20375, and Dept. of Chemistry, The University of Maryland, College Park, MD 20742, USA
D. C. Weber
Affiliation:
Naval Research Laboratory, Washington, D. C. 20375, and Dept. of Chemistry, The University of Maryland, College Park, MD 20742, USA
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Abstract

NMR techniques have been used in graphite intercalation systems for chemical analysis and for determinations of structure, molecular dynamics, exchange kinetics, conductivity and electron concentration. Salient results will be presented. We have been most interested in understanding the reaction

3AsF5 + 2Cn ⇋ 2CnAsF6 + AsF3 (1)

for which a single, extremely narrow 19F NMR line is observed when AsF5 reacts with graphite. In contrast, when the reaction

NO2AsF6(in CH3NO2) + Cn→NO2 ↑ + CnAsF6 (2)

is carried out, followed by addition of the stoichicmetric amount of AsF3, separate spectra for the AsF6 (a broad doublet) and lor AsF3 (a sharp 1:2:1 triplet) are observed, indicating that these two species do not exchange fluorine atoms, and suggesting that eq. (1) is not reversible. The AsF3 triplet gives an order parameter for the molecular thrae fold axis with respect to the graphite c-axis. The carbon-13 spectrum for a fifth stage intercalate of HNO3 shows the 2:2:1 triplet expected if each kind of layer Is resolved.

Type
Research Article
Copyright
Copyright © Materials Research Society 1983

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References

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