Benzoannelated aza-, oxa- and azaoxa[8]circulenes as promising blue organic emitters

Gleb V. Baryshnikov, Rashid R. Valiev, Nataliya N. Karaush, Valentina A. Minaeva, Alexandr N. Sinelnikov, Stephan K. Pedersen, Michael Pittelkow, Boris F. Minaev, Hans Ågren

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

In the present work, we studied the synergetic effect of benzoannelation and NH/O-substitution for enhancing the absorption intensity in a series of novel designed benzoannelated aza- and oxa[8]circulenes. Semi-empirical estimations of the fluorescence rate constants allowed us to determine the most promising fluorophores among all the possible benzoannelated aza-, oxa- and mixed azaoza[8]circulenes. Among them, para-dibenzoannelated [8]circulenes demonstrated the most intense light absorption and emission due to the prevailing role of the linear acene chromophore. Calculated φfl values are in complete agreement with experimental data for a number of already synthesized circulenes. Thus, we believe that the most promising circulenes designed in this study can demonstrate an intensive fluorescence in the case of their successful synthesis, which in turn could be extremely useful for the fabrication of future blue OLEDs. Special attention is devoted to the aromaticity features and peculiarities of the absorption spectra for the two highly-symmetrical (D4h ground state symmetry) π-isoelectronic species as well as the so-called tetrabenzotetraaza[8]circulene and tetrabenzotetraoxa[8]circulene molecules. Both of them are characterized by rich electronic spectra, which can be assigned only by taking into account the vibronic coarse structure of the first electronic absorption band; the 0-1 and 0-2 transitions were found to be active in the absorption spectrum in complete agreement with experimental data obtained for both energy and intensity. The corresponding promotive vibrational modes have been determined and their vibronic activity estimated using the Franck-Condon approximation.

Original languageEnglish
Pages (from-to)28040-28051
Number of pages12
JournalPhysical Chemistry Chemical Physics
Volume18
Issue number40
DOIs
Publication statusPublished - 2016

Fingerprint

Absorption spectra
emitters
absorption spectra
Fluorescence
fluorescence
Fluorophores
Light emission
Crystal symmetry
Organic light emitting diodes (OLED)
Chromophores
Electron transitions
electromagnetic absorption
electronic spectra
Light absorption
Ground state
chromophores
light emission
vibration mode
Rate constants
Substitution reactions

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Baryshnikov, G. V., Valiev, R. R., Karaush, N. N., Minaeva, V. A., Sinelnikov, A. N., Pedersen, S. K., ... Ågren, H. (2016). Benzoannelated aza-, oxa- and azaoxa[8]circulenes as promising blue organic emitters. Physical Chemistry Chemical Physics, 18(40), 28040-28051. https://doi.org/10.1039/c6cp03060b

Benzoannelated aza-, oxa- and azaoxa[8]circulenes as promising blue organic emitters. / Baryshnikov, Gleb V.; Valiev, Rashid R.; Karaush, Nataliya N.; Minaeva, Valentina A.; Sinelnikov, Alexandr N.; Pedersen, Stephan K.; Pittelkow, Michael; Minaev, Boris F.; Ågren, Hans.

In: Physical Chemistry Chemical Physics, Vol. 18, No. 40, 2016, p. 28040-28051.

Research output: Contribution to journalArticle

Baryshnikov, GV, Valiev, RR, Karaush, NN, Minaeva, VA, Sinelnikov, AN, Pedersen, SK, Pittelkow, M, Minaev, BF & Ågren, H 2016, 'Benzoannelated aza-, oxa- and azaoxa[8]circulenes as promising blue organic emitters', Physical Chemistry Chemical Physics, vol. 18, no. 40, pp. 28040-28051. https://doi.org/10.1039/c6cp03060b
Baryshnikov, Gleb V. ; Valiev, Rashid R. ; Karaush, Nataliya N. ; Minaeva, Valentina A. ; Sinelnikov, Alexandr N. ; Pedersen, Stephan K. ; Pittelkow, Michael ; Minaev, Boris F. ; Ågren, Hans. / Benzoannelated aza-, oxa- and azaoxa[8]circulenes as promising blue organic emitters. In: Physical Chemistry Chemical Physics. 2016 ; Vol. 18, No. 40. pp. 28040-28051.
@article{e0b0ac33b07341d9a4ada1d6d3b6c9af,
title = "Benzoannelated aza-, oxa- and azaoxa[8]circulenes as promising blue organic emitters",
abstract = "In the present work, we studied the synergetic effect of benzoannelation and NH/O-substitution for enhancing the absorption intensity in a series of novel designed benzoannelated aza- and oxa[8]circulenes. Semi-empirical estimations of the fluorescence rate constants allowed us to determine the most promising fluorophores among all the possible benzoannelated aza-, oxa- and mixed azaoza[8]circulenes. Among them, para-dibenzoannelated [8]circulenes demonstrated the most intense light absorption and emission due to the prevailing role of the linear acene chromophore. Calculated φfl values are in complete agreement with experimental data for a number of already synthesized circulenes. Thus, we believe that the most promising circulenes designed in this study can demonstrate an intensive fluorescence in the case of their successful synthesis, which in turn could be extremely useful for the fabrication of future blue OLEDs. Special attention is devoted to the aromaticity features and peculiarities of the absorption spectra for the two highly-symmetrical (D4h ground state symmetry) π-isoelectronic species as well as the so-called tetrabenzotetraaza[8]circulene and tetrabenzotetraoxa[8]circulene molecules. Both of them are characterized by rich electronic spectra, which can be assigned only by taking into account the vibronic coarse structure of the first electronic absorption band; the 0-1 and 0-2 transitions were found to be active in the absorption spectrum in complete agreement with experimental data obtained for both energy and intensity. The corresponding promotive vibrational modes have been determined and their vibronic activity estimated using the Franck-Condon approximation.",
author = "Baryshnikov, {Gleb V.} and Valiev, {Rashid R.} and Karaush, {Nataliya N.} and Minaeva, {Valentina A.} and Sinelnikov, {Alexandr N.} and Pedersen, {Stephan K.} and Michael Pittelkow and Minaev, {Boris F.} and Hans {\AA}gren",
year = "2016",
doi = "10.1039/c6cp03060b",
language = "English",
volume = "18",
pages = "28040--28051",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "40",

}

TY - JOUR

T1 - Benzoannelated aza-, oxa- and azaoxa[8]circulenes as promising blue organic emitters

AU - Baryshnikov, Gleb V.

AU - Valiev, Rashid R.

AU - Karaush, Nataliya N.

AU - Minaeva, Valentina A.

AU - Sinelnikov, Alexandr N.

AU - Pedersen, Stephan K.

AU - Pittelkow, Michael

AU - Minaev, Boris F.

AU - Ågren, Hans

PY - 2016

Y1 - 2016

N2 - In the present work, we studied the synergetic effect of benzoannelation and NH/O-substitution for enhancing the absorption intensity in a series of novel designed benzoannelated aza- and oxa[8]circulenes. Semi-empirical estimations of the fluorescence rate constants allowed us to determine the most promising fluorophores among all the possible benzoannelated aza-, oxa- and mixed azaoza[8]circulenes. Among them, para-dibenzoannelated [8]circulenes demonstrated the most intense light absorption and emission due to the prevailing role of the linear acene chromophore. Calculated φfl values are in complete agreement with experimental data for a number of already synthesized circulenes. Thus, we believe that the most promising circulenes designed in this study can demonstrate an intensive fluorescence in the case of their successful synthesis, which in turn could be extremely useful for the fabrication of future blue OLEDs. Special attention is devoted to the aromaticity features and peculiarities of the absorption spectra for the two highly-symmetrical (D4h ground state symmetry) π-isoelectronic species as well as the so-called tetrabenzotetraaza[8]circulene and tetrabenzotetraoxa[8]circulene molecules. Both of them are characterized by rich electronic spectra, which can be assigned only by taking into account the vibronic coarse structure of the first electronic absorption band; the 0-1 and 0-2 transitions were found to be active in the absorption spectrum in complete agreement with experimental data obtained for both energy and intensity. The corresponding promotive vibrational modes have been determined and their vibronic activity estimated using the Franck-Condon approximation.

AB - In the present work, we studied the synergetic effect of benzoannelation and NH/O-substitution for enhancing the absorption intensity in a series of novel designed benzoannelated aza- and oxa[8]circulenes. Semi-empirical estimations of the fluorescence rate constants allowed us to determine the most promising fluorophores among all the possible benzoannelated aza-, oxa- and mixed azaoza[8]circulenes. Among them, para-dibenzoannelated [8]circulenes demonstrated the most intense light absorption and emission due to the prevailing role of the linear acene chromophore. Calculated φfl values are in complete agreement with experimental data for a number of already synthesized circulenes. Thus, we believe that the most promising circulenes designed in this study can demonstrate an intensive fluorescence in the case of their successful synthesis, which in turn could be extremely useful for the fabrication of future blue OLEDs. Special attention is devoted to the aromaticity features and peculiarities of the absorption spectra for the two highly-symmetrical (D4h ground state symmetry) π-isoelectronic species as well as the so-called tetrabenzotetraaza[8]circulene and tetrabenzotetraoxa[8]circulene molecules. Both of them are characterized by rich electronic spectra, which can be assigned only by taking into account the vibronic coarse structure of the first electronic absorption band; the 0-1 and 0-2 transitions were found to be active in the absorption spectrum in complete agreement with experimental data obtained for both energy and intensity. The corresponding promotive vibrational modes have been determined and their vibronic activity estimated using the Franck-Condon approximation.

UR - http://www.scopus.com/inward/record.url?scp=84991660782&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84991660782&partnerID=8YFLogxK

U2 - 10.1039/c6cp03060b

DO - 10.1039/c6cp03060b

M3 - Article

VL - 18

SP - 28040

EP - 28051

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 40

ER -