Stable Nitrogen-Centered Bis(imino)rylene Diradicaloids

Wangdong Zeng, Yongseok Hong, Samara Medina Rivero, Jinseok Kim, José L. Zafra, Hoa Phan, Tullimilli Y. Gopalakrishna, Tun Seng Herng, Jun Ding, Juan Casado, Dongho Kim, Jishan Wu

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)

Abstract

The synthesis of stable open-shell singlet diradicaloids is critical for their practical material application. So far, most reported examples are based on carbon-centered radicals, which are intrinsically reactive, and there are very few examples of stable nitrogen-centered diradicaloids. In this full paper, a series of soluble and stable bis(imino)rylenes up to octarylene were synthesized on the basis of newly developed dibromorylene intermediates. It was found that from hexarylene onward, these quinoidal rylenes showed open-shell singlet ground states and could be thermally populated to paramagnetic triplet aminyl diradicals. They are stable due to efficient spin delocalization onto the rylene backbone as well as kinetic blocking of the aminyl sites by the bulky and electron-deficient 2,4,6-trichlorophenyl groups. They exhibited very different electronic structures, diradical character, excited-state dynamics, one-photon absorption, two-photon absorption, and electrochemical properties from their respective aromatic rylene counterparts. These bis(imino)rylenes represent a rare class of stable, neutral, nitrogen-centered aminyl diradicaloids.

Original languageEnglish
Pages (from-to)4944-4951
Number of pages8
JournalChemistry - A European Journal
Volume24
Issue number19
DOIs
Publication statusPublished - 2018 Apr 3

Bibliographical note

Funding Information:
J.W. acknowledges financial support from the MOE Tier 3 programme (MOE2014-T3-1-004). The work at Yonsei University was supported by Global Research Laboratory (2013K1A1A2A02050183) through the National Research Foundation of Korea. J.C. thanks support from MINECO/FEDER of Spain Government (CTQ2015-69391-P) and S.M.R. thanks the MINECO for a FPI grant.

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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