Resonance Raman Spectroelectrochemistry. 6. Ultraviolet Laser Excitation of the Tetracyanoquinodimethane Dianion

Richard P. Van Duyne; Mary R. Suchanski; Joseph M. Lakovits; Allen R. Siedle; Keith D. Parks; Therese M. Cotton

doi:10.1021/ja00505a004

Resonance Raman Spectroelectrochemistry. 6. Ultraviolet Laser Excitation of the Tetracyanoquinodimethane Dianion

Richard P. Van Duyne^*, Mary R. Suchanski, Joseph M. Lakovits, Allen R. Siedle, Keith D. Parks, Therese M. Cotton

^*Corresponding author for this work

Chemistry

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Abstract

The resonance Raman spectrum has been obtained for the electrogenerated dianion of tetracyanoquinodimethane (TCNQ) upon excitation of its lowest energy electronic transition (λ_max 330 nm) with a frequency doubled, flashlamppumped, Rhodamine 640 dye laser. For comparison we report the normal Raman spectrum of solid Li₂TCNQ.THF. The electron transfer induced frequency shifts for the second reduction step of TCNQ are measured and interpreted using the π-bond order changes determined from SCF-MO-CI and 1NDO/S electronic structure calculations as well as the π-bond length changes determined from a MNDO-SCF-MO calculation. Finally, the TCNQ^2- Raman data is used to identify the oxidation state of TCNQ in the coordination complex [Co(acacen)(py)₂]₂TCNQ.

Original language	English (US)
Pages (from-to)	2832-2837
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	101
Issue number	11
DOIs	https://doi.org/10.1021/ja00505a004
State	Published - 1979

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Resonance Raman Spectroelectrochemistry. 6. Ultraviolet Laser Excitation of the Tetracyanoquinodimethane Dianion",

abstract = "The resonance Raman spectrum has been obtained for the electrogenerated dianion of tetracyanoquinodimethane (TCNQ) upon excitation of its lowest energy electronic transition (λmax 330 nm) with a frequency doubled, flashlamppumped, Rhodamine 640 dye laser. For comparison we report the normal Raman spectrum of solid Li2TCNQ.THF. The electron transfer induced frequency shifts for the second reduction step of TCNQ are measured and interpreted using the π-bond order changes determined from SCF-MO-CI and 1NDO/S electronic structure calculations as well as the π-bond length changes determined from a MNDO-SCF-MO calculation. Finally, the TCNQ2- Raman data is used to identify the oxidation state of TCNQ in the coordination complex [Co(acacen)(py)2]2TCNQ.",

author = "{Van Duyne}, {Richard P.} and Suchanski, {Mary R.} and Lakovits, {Joseph M.} and Siedle, {Allen R.} and Parks, {Keith D.} and Cotton, {Therese M.}",

year = "1979",

doi = "10.1021/ja00505a004",

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volume = "101",

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journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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T1 - Resonance Raman Spectroelectrochemistry. 6. Ultraviolet Laser Excitation of the Tetracyanoquinodimethane Dianion

AU - Van Duyne, Richard P.

AU - Suchanski, Mary R.

AU - Lakovits, Joseph M.

AU - Siedle, Allen R.

AU - Parks, Keith D.

AU - Cotton, Therese M.

PY - 1979

Y1 - 1979

N2 - The resonance Raman spectrum has been obtained for the electrogenerated dianion of tetracyanoquinodimethane (TCNQ) upon excitation of its lowest energy electronic transition (λmax 330 nm) with a frequency doubled, flashlamppumped, Rhodamine 640 dye laser. For comparison we report the normal Raman spectrum of solid Li2TCNQ.THF. The electron transfer induced frequency shifts for the second reduction step of TCNQ are measured and interpreted using the π-bond order changes determined from SCF-MO-CI and 1NDO/S electronic structure calculations as well as the π-bond length changes determined from a MNDO-SCF-MO calculation. Finally, the TCNQ2- Raman data is used to identify the oxidation state of TCNQ in the coordination complex [Co(acacen)(py)2]2TCNQ.

AB - The resonance Raman spectrum has been obtained for the electrogenerated dianion of tetracyanoquinodimethane (TCNQ) upon excitation of its lowest energy electronic transition (λmax 330 nm) with a frequency doubled, flashlamppumped, Rhodamine 640 dye laser. For comparison we report the normal Raman spectrum of solid Li2TCNQ.THF. The electron transfer induced frequency shifts for the second reduction step of TCNQ are measured and interpreted using the π-bond order changes determined from SCF-MO-CI and 1NDO/S electronic structure calculations as well as the π-bond length changes determined from a MNDO-SCF-MO calculation. Finally, the TCNQ2- Raman data is used to identify the oxidation state of TCNQ in the coordination complex [Co(acacen)(py)2]2TCNQ.

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Resonance Raman Spectroelectrochemistry. 6. Ultraviolet Laser Excitation of the Tetracyanoquinodimethane Dianion

Abstract

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