Toward designed singlet fission

Electronic states and photophysics of 1,3-diphenylisobenzofuran

Andrew F. Schwerin, Justin C. Johnson, Millicent B. Smith, Paiboon Sreearunothai, Duška Popović, Jiří Černý, Zdeněk Havias, Irina Paci, Akin Akdag, Matthew K. MacLeod, Xudong Chen, Donald E. David, Mark A Ratner, John R. Miller, Arthur J. Nozik, Josef Michl

Research output: Contribution to journalArticle

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Abstract

Single crystal molecular structure and solution photophysical properties are reported for 1,3-diphenylisobenzofuran (1), of interest as a model compound in studies of singlet fission. For the ground state of 1 and of its radical cation (1+.) and anion (1-.), we report the UV - visible absorption spectra, and for neutral 1, also the magnetic circular dichroism (MCD) and the decomposition of the absorption spectrum into purely polarized components, deduced from fluorescence polarization. These results were used to identify a series of singlet excited states. For the first excited singlet and triplet states of 1, the transient visible absorption spectra, Si → S x and sensitized T1 → Tx, and single exponential lifetimes, τF = ∼5.3 ns and τT = ∼200 μs, are reported. The spectra and lifetimes of Si → S 0 fluorescence and sensitized T1 → Tx absorption of 1 were obtained in a series of solvents, as was the fluorescence quantum yield, ΦF = 0.95-0.99. No phosphorescence has been detected. The first triplet excitation energy of solid 1 (11 400 cm -1) was obtained by electron energy loss spectroscopy, in agreement with previously reported solution values. The fluorescence excitation spectrum suggests an onset of a nonradiative channel at ∼37 000 cm-1. Excitation energies and relative transition intensities are in agreement with those of ab initio (CC2) calculations after an empirical 3000 cm-1 adjustment of the initial state energy to correct differentially for a better quality description of the initial relative to the terminal state of an absorption transition. The interpretation of the MCD spectrum used the semiempirical PPP method, whose results for the S0 → S x spectrum require no empirical adjustment and are otherwise nearly identical with the CC2 results in all respects including the detailed nature of the electronic excitation. The ground state geometry of 1 was also calculated by the MP2, B3LYP, and CAS methods. The calculations provided a prediction of changes of molecular geometry upon excitation or ionization and permitted an interpretation of the spectra in terms of molecular orbitais involved. Computations suggest that 1 can exist as two nearly isoenergetic conformers of C2 or Cs, symmetry. Linear dichroism measurements in stretched polyethylene provide evidence for their existence and show that they orient to different degrees, permitting a separation of their spectra in the region of the purely polarized first absorption band. Their excitation energies are nearly identical, but the Franck-Condon envelopes of their first transition differ to a surprising degree.

Original languageEnglish
Pages (from-to)1457-1473
Number of pages17
JournalJournal of Physical Chemistry A
Volume114
Issue number3
DOIs
Publication statusPublished - 2010

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Electronic states
fission
Excitation energy
Absorption spectra
Fluorescence
electronics
Ground state
excitation
dichroism
absorption spectra
fluorescence
Phosphorescence
Geometry
visible spectrum
Electron energy loss spectroscopy
Polyethylene
Quantum yield
atomic energy levels
Electron transitions
Excited states

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Schwerin, A. F., Johnson, J. C., Smith, M. B., Sreearunothai, P., Popović, D., Černý, J., ... Michl, J. (2010). Toward designed singlet fission: Electronic states and photophysics of 1,3-diphenylisobenzofuran. Journal of Physical Chemistry A, 114(3), 1457-1473. https://doi.org/10.1021/jp907401t

Toward designed singlet fission : Electronic states and photophysics of 1,3-diphenylisobenzofuran. / Schwerin, Andrew F.; Johnson, Justin C.; Smith, Millicent B.; Sreearunothai, Paiboon; Popović, Duška; Černý, Jiří; Havias, Zdeněk; Paci, Irina; Akdag, Akin; MacLeod, Matthew K.; Chen, Xudong; David, Donald E.; Ratner, Mark A; Miller, John R.; Nozik, Arthur J.; Michl, Josef.

In: Journal of Physical Chemistry A, Vol. 114, No. 3, 2010, p. 1457-1473.

Research output: Contribution to journalArticle

Schwerin, AF, Johnson, JC, Smith, MB, Sreearunothai, P, Popović, D, Černý, J, Havias, Z, Paci, I, Akdag, A, MacLeod, MK, Chen, X, David, DE, Ratner, MA, Miller, JR, Nozik, AJ & Michl, J 2010, 'Toward designed singlet fission: Electronic states and photophysics of 1,3-diphenylisobenzofuran', Journal of Physical Chemistry A, vol. 114, no. 3, pp. 1457-1473. https://doi.org/10.1021/jp907401t
Schwerin AF, Johnson JC, Smith MB, Sreearunothai P, Popović D, Černý J et al. Toward designed singlet fission: Electronic states and photophysics of 1,3-diphenylisobenzofuran. Journal of Physical Chemistry A. 2010;114(3):1457-1473. https://doi.org/10.1021/jp907401t
Schwerin, Andrew F. ; Johnson, Justin C. ; Smith, Millicent B. ; Sreearunothai, Paiboon ; Popović, Duška ; Černý, Jiří ; Havias, Zdeněk ; Paci, Irina ; Akdag, Akin ; MacLeod, Matthew K. ; Chen, Xudong ; David, Donald E. ; Ratner, Mark A ; Miller, John R. ; Nozik, Arthur J. ; Michl, Josef. / Toward designed singlet fission : Electronic states and photophysics of 1,3-diphenylisobenzofuran. In: Journal of Physical Chemistry A. 2010 ; Vol. 114, No. 3. pp. 1457-1473.
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AU - Schwerin, Andrew F.

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AU - Sreearunothai, Paiboon

AU - Popović, Duška

AU - Černý, Jiří

AU - Havias, Zdeněk

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AU - Akdag, Akin

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AU - Chen, Xudong

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N2 - Single crystal molecular structure and solution photophysical properties are reported for 1,3-diphenylisobenzofuran (1), of interest as a model compound in studies of singlet fission. For the ground state of 1 and of its radical cation (1+.) and anion (1-.), we report the UV - visible absorption spectra, and for neutral 1, also the magnetic circular dichroism (MCD) and the decomposition of the absorption spectrum into purely polarized components, deduced from fluorescence polarization. These results were used to identify a series of singlet excited states. For the first excited singlet and triplet states of 1, the transient visible absorption spectra, Si → S x and sensitized T1 → Tx, and single exponential lifetimes, τF = ∼5.3 ns and τT = ∼200 μs, are reported. The spectra and lifetimes of Si → S 0 fluorescence and sensitized T1 → Tx absorption of 1 were obtained in a series of solvents, as was the fluorescence quantum yield, ΦF = 0.95-0.99. No phosphorescence has been detected. The first triplet excitation energy of solid 1 (11 400 cm -1) was obtained by electron energy loss spectroscopy, in agreement with previously reported solution values. The fluorescence excitation spectrum suggests an onset of a nonradiative channel at ∼37 000 cm-1. Excitation energies and relative transition intensities are in agreement with those of ab initio (CC2) calculations after an empirical 3000 cm-1 adjustment of the initial state energy to correct differentially for a better quality description of the initial relative to the terminal state of an absorption transition. The interpretation of the MCD spectrum used the semiempirical PPP method, whose results for the S0 → S x spectrum require no empirical adjustment and are otherwise nearly identical with the CC2 results in all respects including the detailed nature of the electronic excitation. The ground state geometry of 1 was also calculated by the MP2, B3LYP, and CAS methods. The calculations provided a prediction of changes of molecular geometry upon excitation or ionization and permitted an interpretation of the spectra in terms of molecular orbitais involved. Computations suggest that 1 can exist as two nearly isoenergetic conformers of C2 or Cs, symmetry. Linear dichroism measurements in stretched polyethylene provide evidence for their existence and show that they orient to different degrees, permitting a separation of their spectra in the region of the purely polarized first absorption band. Their excitation energies are nearly identical, but the Franck-Condon envelopes of their first transition differ to a surprising degree.

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