DOI: 10.1063/1.437662. The vibrational and electronic spectra of the mono-, di-, and trianon salts of TCNQ

The vibrational and electronic spectra of the mono-, di-, and trianon salts of TCNQ

10.1063/1.437662

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The vibrational and electronic spectra for the sodium mono-, di-, and trianion salts of TCNQ prepared in vacuo by solvent-free vapor codeposition methods, have been measured. These data, combined with published vibrational assignments for neutral TCNQ and the monoanion salts of TCNQ, have permitted an empirical analysis of the effect of increasing electronic charge on the π- bonding of this conjugated system. Thus, empirical molecular force constants determined from new vibrational assignments, which are somewhat tentative in the case of the di- and trianion, indicate a regular transition of the p-quinoid ring system of TCNQ0 to a benzenoid system for TCNQ3−. Simultaneously, the C≡N and C≡C bonds of the TCNQ wings are considerably reduced in strength while the wing C––C bonds gain double bond character eventually surpassing the original C=C bonds in strength in the case of TCNQ3−. The dianion salt, Na2TCNQ, is colorless while the trianion salt, Na3TCNQ, is golden yellow but there is little evidence in either the visible or infrared spectra to suggest that these salts are other than insulators. The vibrational data are indicative of a severe distortion of the anion in Na2TCNQ and, especially, Na3TCNQ.

Bibliography

Khatkale, M. S., & Devlin, J. P. (1979). The vibrational and electronic spectra of the mono-, di-, and trianon salts of TCNQ. The Journal of Chemical Physics, 70(4), 1851â1859.

Authors 2

Murlidhar S. Khatkale (first)
J. Paul Devlin (additional)

References 27 Referenced 137

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Dates

Type	When
Created	22 years, 6 months ago (Feb. 27, 2003, 5:52 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 2:24 p.m.)
Indexed	2 months ago (July 2, 2025, 1:29 p.m.)
Issued	46 years, 6 months ago (Feb. 15, 1979)
Published	46 years, 6 months ago (Feb. 15, 1979)
Published Print	46 years, 6 months ago (Feb. 15, 1979)

Funders 0

None

BibTeX

@article{Khatkale_1979, title={The vibrational and electronic spectra of the mono-, di-, and trianon salts of TCNQ}, volume={70}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.437662}, DOI={10.1063/1.437662}, number={4}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Khatkale, Murlidhar S. and Devlin, J. Paul}, year={1979}, month=feb, pages={1851–1859} }

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  "abstract": "<jats:p>The vibrational and electronic spectra for the sodium mono-, di-, and trianion salts of TCNQ prepared in\u2008vacuo by solvent-free vapor codeposition methods, have been measured. These data, combined with published vibrational assignments for neutral TCNQ and the monoanion salts of TCNQ, have permitted an empirical analysis of the effect of increasing electronic charge on the \u03c0- bonding of this conjugated system. Thus, empirical molecular force constants determined from new vibrational assignments, which are somewhat tentative in the case of the di- and trianion, indicate a regular transition of the p-quinoid ring system of TCNQ0 to a benzenoid system for TCNQ3\u2212. Simultaneously, the C\u2261N and C\u2261C bonds of the TCNQ wings are considerably reduced in strength while the wing C\u2013\u2013C bonds gain double bond character eventually surpassing the original C=C bonds in strength in the case of TCNQ3\u2212. The dianion salt, Na2TCNQ, is colorless while the trianion salt, Na3TCNQ, is golden yellow but there is little evidence in either the visible or infrared spectra to suggest that these salts are other than insulators. The vibrational data are indicative of a severe distortion of the anion in Na2TCNQ and, especially, Na3TCNQ.</jats:p>",
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