Pre-resonance Raman and IR absorption spectroscopy of imidazophenazine and its derivatives: Experimental and ab initio study

V. A. Karachevtsev, E. S. Zarudnev, A. Yu Glamazda, A. M. Plokhotnichenko, V. N. Zozulya, S. G. Stepanian, Ludwik Adamowicz

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The pre-resonance Raman and IR absorption spectroscopy techniques have been applied to study the influence of substitutes in the imidazole ring of imidazo-[4,5-d]-phenazine (F1) on its vibrational structure. The following F1 derivatives in the KBr pellets have been investigated: 2-methylimidazo-[4,5-d]-phenazine (F2), 2-trifluoridemethylimidazo-[4,5-d]-phenazine (F3), and 1,2,3-triazole-[4,5-d]-phenazine (F4). The experimental Raman and IR data were analyzed using the harmonic frequencies, the IR intensities, and the pre-resonance Raman activities calculated at the DFT(B3LYP)/6-31++G** level of theory. We found a good agreement between the observed and the calculated spectra for all the normal modes except the ones attributed to the vibrations of the NH group. These latter modes are the most affected by the strong intermolecular interactions that occur in the solid samples. The bending ring vibrations dominate in the spectra of all compounds studied. The vibrational structure of the F1 derivatives is similar to that of the parent compound, though for each compound, characteristic bands also appear in the spectrum. Among the F1 derivatives, the vibrational spectrum of the F4 compound where the C atom of the imidazole ring is replaced by the N atom, changes the most from the spectrum of the parent compound. The nature of the six lowest electronic transitions to the S1-S6 states in the F1-F4 compounds and the forms of the π, π* and n orbitals involved in the transitions were also determined. This revealed that the first singlet excited state in all studied compounds corresponds to a π → π* transition.

Original languageEnglish (US)
Pages (from-to)71-81
Number of pages11
JournalVibrational Spectroscopy
Volume47
Issue number2
DOIs
StatePublished - Jul 17 2008

Fingerprint

Absorption spectroscopy
Infrared spectroscopy
Derivatives
Atoms
Triazoles
Vibrational spectra
Excited states
Discrete Fourier transforms
phenazine
imidazole

Keywords

  • DFT calculation
  • Dyes
  • IR absorption spectroscopy
  • Pre-resonance Raman
  • Vibrational spectroscopy

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy

Cite this

Pre-resonance Raman and IR absorption spectroscopy of imidazophenazine and its derivatives : Experimental and ab initio study. / Karachevtsev, V. A.; Zarudnev, E. S.; Glamazda, A. Yu; Plokhotnichenko, A. M.; Zozulya, V. N.; Stepanian, S. G.; Adamowicz, Ludwik.

In: Vibrational Spectroscopy, Vol. 47, No. 2, 17.07.2008, p. 71-81.

Research output: Contribution to journalArticle

Karachevtsev, V. A. ; Zarudnev, E. S. ; Glamazda, A. Yu ; Plokhotnichenko, A. M. ; Zozulya, V. N. ; Stepanian, S. G. ; Adamowicz, Ludwik. / Pre-resonance Raman and IR absorption spectroscopy of imidazophenazine and its derivatives : Experimental and ab initio study. In: Vibrational Spectroscopy. 2008 ; Vol. 47, No. 2. pp. 71-81.
@article{cf85fdaf99774cb79b6acb75fef295a0,
title = "Pre-resonance Raman and IR absorption spectroscopy of imidazophenazine and its derivatives: Experimental and ab initio study",
abstract = "The pre-resonance Raman and IR absorption spectroscopy techniques have been applied to study the influence of substitutes in the imidazole ring of imidazo-[4,5-d]-phenazine (F1) on its vibrational structure. The following F1 derivatives in the KBr pellets have been investigated: 2-methylimidazo-[4,5-d]-phenazine (F2), 2-trifluoridemethylimidazo-[4,5-d]-phenazine (F3), and 1,2,3-triazole-[4,5-d]-phenazine (F4). The experimental Raman and IR data were analyzed using the harmonic frequencies, the IR intensities, and the pre-resonance Raman activities calculated at the DFT(B3LYP)/6-31++G** level of theory. We found a good agreement between the observed and the calculated spectra for all the normal modes except the ones attributed to the vibrations of the NH group. These latter modes are the most affected by the strong intermolecular interactions that occur in the solid samples. The bending ring vibrations dominate in the spectra of all compounds studied. The vibrational structure of the F1 derivatives is similar to that of the parent compound, though for each compound, characteristic bands also appear in the spectrum. Among the F1 derivatives, the vibrational spectrum of the F4 compound where the C atom of the imidazole ring is replaced by the N atom, changes the most from the spectrum of the parent compound. The nature of the six lowest electronic transitions to the S1-S6 states in the F1-F4 compounds and the forms of the π, π* and n orbitals involved in the transitions were also determined. This revealed that the first singlet excited state in all studied compounds corresponds to a π → π* transition.",
keywords = "DFT calculation, Dyes, IR absorption spectroscopy, Pre-resonance Raman, Vibrational spectroscopy",
author = "Karachevtsev, {V. A.} and Zarudnev, {E. S.} and Glamazda, {A. Yu} and Plokhotnichenko, {A. M.} and Zozulya, {V. N.} and Stepanian, {S. G.} and Ludwik Adamowicz",
year = "2008",
month = "7",
day = "17",
doi = "10.1016/j.vibspec.2008.02.008",
language = "English (US)",
volume = "47",
pages = "71--81",
journal = "Vibrational Spectroscopy",
issn = "0924-2031",
publisher = "Elsevier",
number = "2",

}

TY - JOUR

T1 - Pre-resonance Raman and IR absorption spectroscopy of imidazophenazine and its derivatives

T2 - Experimental and ab initio study

AU - Karachevtsev, V. A.

AU - Zarudnev, E. S.

AU - Glamazda, A. Yu

AU - Plokhotnichenko, A. M.

AU - Zozulya, V. N.

AU - Stepanian, S. G.

AU - Adamowicz, Ludwik

PY - 2008/7/17

Y1 - 2008/7/17

N2 - The pre-resonance Raman and IR absorption spectroscopy techniques have been applied to study the influence of substitutes in the imidazole ring of imidazo-[4,5-d]-phenazine (F1) on its vibrational structure. The following F1 derivatives in the KBr pellets have been investigated: 2-methylimidazo-[4,5-d]-phenazine (F2), 2-trifluoridemethylimidazo-[4,5-d]-phenazine (F3), and 1,2,3-triazole-[4,5-d]-phenazine (F4). The experimental Raman and IR data were analyzed using the harmonic frequencies, the IR intensities, and the pre-resonance Raman activities calculated at the DFT(B3LYP)/6-31++G** level of theory. We found a good agreement between the observed and the calculated spectra for all the normal modes except the ones attributed to the vibrations of the NH group. These latter modes are the most affected by the strong intermolecular interactions that occur in the solid samples. The bending ring vibrations dominate in the spectra of all compounds studied. The vibrational structure of the F1 derivatives is similar to that of the parent compound, though for each compound, characteristic bands also appear in the spectrum. Among the F1 derivatives, the vibrational spectrum of the F4 compound where the C atom of the imidazole ring is replaced by the N atom, changes the most from the spectrum of the parent compound. The nature of the six lowest electronic transitions to the S1-S6 states in the F1-F4 compounds and the forms of the π, π* and n orbitals involved in the transitions were also determined. This revealed that the first singlet excited state in all studied compounds corresponds to a π → π* transition.

AB - The pre-resonance Raman and IR absorption spectroscopy techniques have been applied to study the influence of substitutes in the imidazole ring of imidazo-[4,5-d]-phenazine (F1) on its vibrational structure. The following F1 derivatives in the KBr pellets have been investigated: 2-methylimidazo-[4,5-d]-phenazine (F2), 2-trifluoridemethylimidazo-[4,5-d]-phenazine (F3), and 1,2,3-triazole-[4,5-d]-phenazine (F4). The experimental Raman and IR data were analyzed using the harmonic frequencies, the IR intensities, and the pre-resonance Raman activities calculated at the DFT(B3LYP)/6-31++G** level of theory. We found a good agreement between the observed and the calculated spectra for all the normal modes except the ones attributed to the vibrations of the NH group. These latter modes are the most affected by the strong intermolecular interactions that occur in the solid samples. The bending ring vibrations dominate in the spectra of all compounds studied. The vibrational structure of the F1 derivatives is similar to that of the parent compound, though for each compound, characteristic bands also appear in the spectrum. Among the F1 derivatives, the vibrational spectrum of the F4 compound where the C atom of the imidazole ring is replaced by the N atom, changes the most from the spectrum of the parent compound. The nature of the six lowest electronic transitions to the S1-S6 states in the F1-F4 compounds and the forms of the π, π* and n orbitals involved in the transitions were also determined. This revealed that the first singlet excited state in all studied compounds corresponds to a π → π* transition.

KW - DFT calculation

KW - Dyes

KW - IR absorption spectroscopy

KW - Pre-resonance Raman

KW - Vibrational spectroscopy

UR - http://www.scopus.com/inward/record.url?scp=44649132559&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=44649132559&partnerID=8YFLogxK

U2 - 10.1016/j.vibspec.2008.02.008

DO - 10.1016/j.vibspec.2008.02.008

M3 - Article

AN - SCOPUS:44649132559

VL - 47

SP - 71

EP - 81

JO - Vibrational Spectroscopy

JF - Vibrational Spectroscopy

SN - 0924-2031

IS - 2

ER -