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Fluorenyl radicals stabilized by donor-π-radical conjugation be-tween nitrogen atoms and carbon radicals
  • Shaoqiang Dong,
  • Zekun Tong,
  • Xinfang Zhang
Shaoqiang Dong
Tianjin University

Corresponding Author:[email protected]

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Zekun Tong
Tianjin University
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Xinfang Zhang
Tianjin University
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Abstract

A design strategy towards stable fluorenyl radicals (FRs) is established by introducing donor-π-radical (D-π-R) conjugation between amine N atoms and FR centers through phenyl or 9-anthryl moieties. Four FRs with or without N atom containing protecting groups were designed and synthesized for comparison. X-ray crystallographic analysis displayed planar fluorenyl skeletons of CDP-FR and MA-FR, which form large dihedral angles with protecting groups. Even though, the increased bond-order of C-C and C-N bond be-tween radical center and N atoms by Wiberg bond analysis of all FRs confirmed the D-π-R conjugation. Time-dependent DFT calcula-tions based on frontier molecular orbital analysis further revealed the contribution of D-π-R structures as donor-acceptor effect on the lowest energy absorptions of carbazole and diphenylamine substituted CDP-FR and DPAA-FR. Therefore, beneficial from D-π-R conjugations, CDP-FR and DPAA-FR showed better photo-stability than TP-FR and MA-FR. Our study here provides a new strategy to design and synthesize persistent stable monoradicals.
24 Sep 2024Submitted to Chinese Journal of Chemistry
27 Sep 2024Submission Checks Completed
27 Sep 2024Assigned to Editor
27 Sep 2024Review(s) Completed, Editorial Evaluation Pending
30 Sep 2024Reviewer(s) Assigned