The computational and experimental investigations of photophysical and spectroscopic properties of BF2 dipyrromethene complexes

R. R. Valiev, A. N. Sinelnikov, Y. V. Aksenova, R. T. Kuznetsova, M. B. Berezin, A. S. Semeikin, V. N. Cherepanov

Результат исследований: Материалы для журналаСтатья

22 Цитирования (Scopus)

Выдержка

The electronic excited states of BF2 dipyrromethene (2BrDPM, DPMI, DPMII, PM567 and 4PhDPM) complexes were investigated using the extended multi-configuration quasi-degenerate at the second order of perturbation theory (XMCQDPT2) and the second-order approximate coupled-cluster (CC2) methods. The excitation energies calculated by CC2 are significantly overestimated by 0.42-0.59 eV because of the substantial contributions of double excitation levels to excited states (>10%). However, the calculated XMCQDPT2 excitation energies agree well with experimental ones within the accuracy 0.11-0.20 eV. The very low lasing efficiency (7.8-8.4%) of 4PhDPM compound was explained by the T1 → T4 and T1 → T5 reabsorptions at XMCQDPT2 level of theory. The molecular photonics of pyrromethenes are studied using a combination of the first-principle and semi-empirical calculations. The main mechanism for the deactivation of the energy of the first singlet excited electronic state is the radiative electronic transition for DPMI, DPMII, PM567 and 4PhDPM compounds. Also, the main mechanism for the quenching of fluorescence in considered complexes (except DPMII compound) is the internal conversion. The processes of the internal conversion and intersystem crossing compete with each other in DPMII compound. The measured and calculated fluorescence quantum yields agree well for all considered molecules.

Язык оригиналаАнглийский
Страницы (с-по)323-329
Число страниц7
ЖурналSpectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
Том117
DOI
СостояниеОпубликовано - 1 янв 2014

Отпечаток

Excitation energy
Excited states
Fluorescence
Electronic states
Quantum yield
Photonics
excitation
internal conversion
Quenching
Molecules
electronics
fluorescence
deactivation
lasing
energy
perturbation theory
quenching
dipyrromethene
pyrromethene 567
photonics

ASJC Scopus subject areas

  • Analytical Chemistry
  • Atomic and Molecular Physics, and Optics
  • Instrumentation
  • Spectroscopy

Цитировать

The computational and experimental investigations of photophysical and spectroscopic properties of BF2 dipyrromethene complexes. / Valiev, R. R.; Sinelnikov, A. N.; Aksenova, Y. V.; Kuznetsova, R. T.; Berezin, M. B.; Semeikin, A. S.; Cherepanov, V. N.

В: Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, Том 117, 01.01.2014, стр. 323-329.

Результат исследований: Материалы для журналаСтатья

Valiev, R. R. ; Sinelnikov, A. N. ; Aksenova, Y. V. ; Kuznetsova, R. T. ; Berezin, M. B. ; Semeikin, A. S. ; Cherepanov, V. N. / The computational and experimental investigations of photophysical and spectroscopic properties of BF2 dipyrromethene complexes. В: Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy. 2014 ; Том 117. стр. 323-329.
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T1 - The computational and experimental investigations of photophysical and spectroscopic properties of BF2 dipyrromethene complexes

AU - Valiev, R. R.

AU - Sinelnikov, A. N.

AU - Aksenova, Y. V.

AU - Kuznetsova, R. T.

AU - Berezin, M. B.

AU - Semeikin, A. S.

AU - Cherepanov, V. N.

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N2 - The electronic excited states of BF2 dipyrromethene (2BrDPM, DPMI, DPMII, PM567 and 4PhDPM) complexes were investigated using the extended multi-configuration quasi-degenerate at the second order of perturbation theory (XMCQDPT2) and the second-order approximate coupled-cluster (CC2) methods. The excitation energies calculated by CC2 are significantly overestimated by 0.42-0.59 eV because of the substantial contributions of double excitation levels to excited states (>10%). However, the calculated XMCQDPT2 excitation energies agree well with experimental ones within the accuracy 0.11-0.20 eV. The very low lasing efficiency (7.8-8.4%) of 4PhDPM compound was explained by the T1 → T4 and T1 → T5 reabsorptions at XMCQDPT2 level of theory. The molecular photonics of pyrromethenes are studied using a combination of the first-principle and semi-empirical calculations. The main mechanism for the deactivation of the energy of the first singlet excited electronic state is the radiative electronic transition for DPMI, DPMII, PM567 and 4PhDPM compounds. Also, the main mechanism for the quenching of fluorescence in considered complexes (except DPMII compound) is the internal conversion. The processes of the internal conversion and intersystem crossing compete with each other in DPMII compound. The measured and calculated fluorescence quantum yields agree well for all considered molecules.

AB - The electronic excited states of BF2 dipyrromethene (2BrDPM, DPMI, DPMII, PM567 and 4PhDPM) complexes were investigated using the extended multi-configuration quasi-degenerate at the second order of perturbation theory (XMCQDPT2) and the second-order approximate coupled-cluster (CC2) methods. The excitation energies calculated by CC2 are significantly overestimated by 0.42-0.59 eV because of the substantial contributions of double excitation levels to excited states (>10%). However, the calculated XMCQDPT2 excitation energies agree well with experimental ones within the accuracy 0.11-0.20 eV. The very low lasing efficiency (7.8-8.4%) of 4PhDPM compound was explained by the T1 → T4 and T1 → T5 reabsorptions at XMCQDPT2 level of theory. The molecular photonics of pyrromethenes are studied using a combination of the first-principle and semi-empirical calculations. The main mechanism for the deactivation of the energy of the first singlet excited electronic state is the radiative electronic transition for DPMI, DPMII, PM567 and 4PhDPM compounds. Also, the main mechanism for the quenching of fluorescence in considered complexes (except DPMII compound) is the internal conversion. The processes of the internal conversion and intersystem crossing compete with each other in DPMII compound. The measured and calculated fluorescence quantum yields agree well for all considered molecules.

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KW - Intersystem crossing

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