Competition between Singlet Fission and Spin-Orbit-Induced Intersystem Crossing in Anthanthrene and Anthanthrone Derivatives

Youn Jue Bae, Matthew D. Krzyaniak, Marek B. Majewski, Maude Desroches, Jean François Morin, Yi-Lin Wu, Michael R. Wasielewski*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

12 Scopus citations


Singlet and triplet excited-state dynamics of anthanthrene and anthanthrone derivatives in solution are studied. Triisopropylsilyl- (TIPS) or H-terminated ethynyl groups are used to tune the singlet and triplet energies to enable their potential applications in singlet fission and triplet fusion processes. Time-resolved optical and electron paramagnetic resonance (EPR) spectroscopies are used to obtain a mechanistic understanding of triplet formation. The anthanthrene derivatives form triplet states efficiently at a rate (ca. 107 s−1) comparable to radiative singlet fluorescence processes with approximately 30 % triplet yields, despite their large S1-T1 energy gap (>1 eV) and the lack of carbonyl groups. In contrast, anthanthrone has a higher triplet yield (50±10 %) with a faster intersystem crossing rate (2.7 * 108 s−1) because of the n-π* character of the S1←S0 transition. Analysis of time-resolved spin-polarized EPR spectra of these compounds reveals that the triplet states are primarily generated by the spin-orbit-induced intersystem crossing mechanism. However, at high concentrations, the EPR spectrum of the 4,6,10,14-tetrakis(TIPS-ethynyl)anthanthrene triplet state shows a significant contribution from a non-Boltzmann population of the ms=0 spin sublevel, which is characteristic of triplet formation by singlet fission.

Original languageEnglish (US)
Pages (from-to)1432-1438
Number of pages7
Issue number9
StatePublished - Sep 1 2019


  • anthanthrene
  • anthanthrone
  • photochemistry
  • singlet fission
  • spin-orbit intersystem crossing

ASJC Scopus subject areas

  • General Chemistry


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