Two-electron transfer stabilized by excited-state aromatization

Jinseok Kim, Juwon Oh, Seongchul Park, Jose L. Zafra, Justin R. DeFrancisco, David Casanova, Manho Lim, John D. Tovar, Juan Casado, Dongho Kim

Research output: Contribution to journalArticle

Abstract

The scientific significance of excited-state aromaticity concerns with the elucidation of processes and properties in the excited states. Here, we focus on TMTQ, an oligomer composed of a central 1,6-methano[10]annulene and 5-dicyanomethyl-thiophene peripheries (acceptor-donor-acceptor system), and investigate a two-electron transfer process dominantly stabilized by an aromatization in the low-energy lying excited state. Our spectroscopic measurements quantitatively observe the shift of two π-electrons between donor and acceptors. It is revealed that this two-electron transfer process accompanies the excited-state aromatization, producing a Baird aromatic 8π core annulene in TMTQ. Biradical character on each terminal dicyanomethylene group of TMTQ allows a pseudo triplet-like configuration on the 8π core annulene with multiexcitonic nature, which stabilizes the energetically unfavorable two-charge separated state by the formation of Baird aromatic core annulene. This finding provides a comprehensive understanding of the role of excited-state aromaticity and insight to designing functional photoactive materials.

Original languageEnglish
Article number4983
JournalNature communications
Volume10
Issue number1
DOIs
Publication statusPublished - 2019 Dec 1

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

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    Kim, J., Oh, J., Park, S., Zafra, J. L., DeFrancisco, J. R., Casanova, D., Lim, M., Tovar, J. D., Casado, J., & Kim, D. (2019). Two-electron transfer stabilized by excited-state aromatization. Nature communications, 10(1), [4983]. https://doi.org/10.1038/s41467-019-12986-w