Tuning aryl, hydrazine radical cation electronic interactions using substitutent effects

Guadalupe Valverde-Aguilar, Xianghuai Wang, Edward Plummer, Jenny V. Lockard, Jeffrey I. Zink, Yun Luo, Michael N. Weaver, Stephen F. Nelsen

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

Absorption spectra for 2,3-diaryl-2,3-diazabicyclo[2.2.2]octane radical cations (2(X)̇+) and for their monoaryl analogues 2-tert-butyl-3-aryl-2,3-diazabicyclo[2.2.2]octane radical cations (1(X) ̇+) having para chloro, bromo, iodo, cyano, phenyl, and nitro substituents are reported and compared with those for the previously reported 1- and 2(H)̇+ and 1- and 2(OMe)̇+. The calculated geometries and optical absorption spectra for 2(Cl)̇+ demonstrate that P-C6H4Cl lies between p-C6H 4OMe and C6H5 in its ability to stabilize the lowest energy optical transition of the radical cation, which involves electron donation from the aryl groups toward the π*(NN)+-centered singly occupied molecular orbital of 2(X)̇+. Resonance Raman spectral determination of the reorganization energy for their lowest energy transitions (λvsym) increase in the same order, having values of 1420, 5300, and 6000 cm-1 for X = H, Cl, and OMe, respectively. A neighboring orbital analysis using Koopmans-based calculations of relative orbital energies indicates that the diabatic aryl π-centered molecular orbital that interacts with the dinitrogen π system lies closest in energy to the bonding π(NN)-centered orbital and has an electronic coupling with it of about 9200 ± 600 cm-1, which does not vary regularly with electron donating power of the X substituent.

Original languageEnglish (US)
Pages (from-to)7332-7341
Number of pages10
JournalJournal of Physical Chemistry A
Volume112
Issue number32
DOIs
StatePublished - Aug 14 2008

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hydrazine
hydrazines
Cations
Tuning
tuning
Molecular orbitals
cations
Absorption spectra
electronics
octanes
Optical transitions
Electrons
orbitals
interactions
molecular orbitals
Light absorption
energy
absorption spectra
optical transition
Geometry

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Valverde-Aguilar, G., Wang, X., Plummer, E., Lockard, J. V., Zink, J. I., Luo, Y., ... Nelsen, S. F. (2008). Tuning aryl, hydrazine radical cation electronic interactions using substitutent effects. Journal of Physical Chemistry A, 112(32), 7332-7341. https://doi.org/10.1021/jp7120005
Valverde-Aguilar, Guadalupe ; Wang, Xianghuai ; Plummer, Edward ; Lockard, Jenny V. ; Zink, Jeffrey I. ; Luo, Yun ; Weaver, Michael N. ; Nelsen, Stephen F. / Tuning aryl, hydrazine radical cation electronic interactions using substitutent effects. In: Journal of Physical Chemistry A. 2008 ; Vol. 112, No. 32. pp. 7332-7341.
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title = "Tuning aryl, hydrazine radical cation electronic interactions using substitutent effects",
abstract = "Absorption spectra for 2,3-diaryl-2,3-diazabicyclo[2.2.2]octane radical cations (2(X)̇+) and for their monoaryl analogues 2-tert-butyl-3-aryl-2,3-diazabicyclo[2.2.2]octane radical cations (1(X) ̇+) having para chloro, bromo, iodo, cyano, phenyl, and nitro substituents are reported and compared with those for the previously reported 1- and 2(H)̇+ and 1- and 2(OMe)̇+. The calculated geometries and optical absorption spectra for 2(Cl)̇+ demonstrate that P-C6H4Cl lies between p-C6H 4OMe and C6H5 in its ability to stabilize the lowest energy optical transition of the radical cation, which involves electron donation from the aryl groups toward the π*(NN)+-centered singly occupied molecular orbital of 2(X)̇+. Resonance Raman spectral determination of the reorganization energy for their lowest energy transitions (λvsym) increase in the same order, having values of 1420, 5300, and 6000 cm-1 for X = H, Cl, and OMe, respectively. A neighboring orbital analysis using Koopmans-based calculations of relative orbital energies indicates that the diabatic aryl π-centered molecular orbital that interacts with the dinitrogen π system lies closest in energy to the bonding π(NN)-centered orbital and has an electronic coupling with it of about 9200 ± 600 cm-1, which does not vary regularly with electron donating power of the X substituent.",
author = "Guadalupe Valverde-Aguilar and Xianghuai Wang and Edward Plummer and Lockard, {Jenny V.} and Zink, {Jeffrey I.} and Yun Luo and Weaver, {Michael N.} and Nelsen, {Stephen F.}",
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Valverde-Aguilar, G, Wang, X, Plummer, E, Lockard, JV, Zink, JI, Luo, Y, Weaver, MN & Nelsen, SF 2008, 'Tuning aryl, hydrazine radical cation electronic interactions using substitutent effects', Journal of Physical Chemistry A, vol. 112, no. 32, pp. 7332-7341. https://doi.org/10.1021/jp7120005

Tuning aryl, hydrazine radical cation electronic interactions using substitutent effects. / Valverde-Aguilar, Guadalupe; Wang, Xianghuai; Plummer, Edward; Lockard, Jenny V.; Zink, Jeffrey I.; Luo, Yun; Weaver, Michael N.; Nelsen, Stephen F.

In: Journal of Physical Chemistry A, Vol. 112, No. 32, 14.08.2008, p. 7332-7341.

Research output: Contribution to journalArticle

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T1 - Tuning aryl, hydrazine radical cation electronic interactions using substitutent effects

AU - Valverde-Aguilar, Guadalupe

AU - Wang, Xianghuai

AU - Plummer, Edward

AU - Lockard, Jenny V.

AU - Zink, Jeffrey I.

AU - Luo, Yun

AU - Weaver, Michael N.

AU - Nelsen, Stephen F.

PY - 2008/8/14

Y1 - 2008/8/14

N2 - Absorption spectra for 2,3-diaryl-2,3-diazabicyclo[2.2.2]octane radical cations (2(X)̇+) and for their monoaryl analogues 2-tert-butyl-3-aryl-2,3-diazabicyclo[2.2.2]octane radical cations (1(X) ̇+) having para chloro, bromo, iodo, cyano, phenyl, and nitro substituents are reported and compared with those for the previously reported 1- and 2(H)̇+ and 1- and 2(OMe)̇+. The calculated geometries and optical absorption spectra for 2(Cl)̇+ demonstrate that P-C6H4Cl lies between p-C6H 4OMe and C6H5 in its ability to stabilize the lowest energy optical transition of the radical cation, which involves electron donation from the aryl groups toward the π*(NN)+-centered singly occupied molecular orbital of 2(X)̇+. Resonance Raman spectral determination of the reorganization energy for their lowest energy transitions (λvsym) increase in the same order, having values of 1420, 5300, and 6000 cm-1 for X = H, Cl, and OMe, respectively. A neighboring orbital analysis using Koopmans-based calculations of relative orbital energies indicates that the diabatic aryl π-centered molecular orbital that interacts with the dinitrogen π system lies closest in energy to the bonding π(NN)-centered orbital and has an electronic coupling with it of about 9200 ± 600 cm-1, which does not vary regularly with electron donating power of the X substituent.

AB - Absorption spectra for 2,3-diaryl-2,3-diazabicyclo[2.2.2]octane radical cations (2(X)̇+) and for their monoaryl analogues 2-tert-butyl-3-aryl-2,3-diazabicyclo[2.2.2]octane radical cations (1(X) ̇+) having para chloro, bromo, iodo, cyano, phenyl, and nitro substituents are reported and compared with those for the previously reported 1- and 2(H)̇+ and 1- and 2(OMe)̇+. The calculated geometries and optical absorption spectra for 2(Cl)̇+ demonstrate that P-C6H4Cl lies between p-C6H 4OMe and C6H5 in its ability to stabilize the lowest energy optical transition of the radical cation, which involves electron donation from the aryl groups toward the π*(NN)+-centered singly occupied molecular orbital of 2(X)̇+. Resonance Raman spectral determination of the reorganization energy for their lowest energy transitions (λvsym) increase in the same order, having values of 1420, 5300, and 6000 cm-1 for X = H, Cl, and OMe, respectively. A neighboring orbital analysis using Koopmans-based calculations of relative orbital energies indicates that the diabatic aryl π-centered molecular orbital that interacts with the dinitrogen π system lies closest in energy to the bonding π(NN)-centered orbital and has an electronic coupling with it of about 9200 ± 600 cm-1, which does not vary regularly with electron donating power of the X substituent.

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