4.8 Article

A Self-Assembled Homochiral Radical Cage with Paramagnetic Behaviors

期刊

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 18, 页码 9852-9858

出版社

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202100655

关键词

dynamic covalent chemistry; homochirality; organic cages; organic radicals; self-assembly

资金

  1. National Natural Science Foundation of China [21772173, 91856116, 21722304, 21922108]
  2. Natural Science Foundation of Zhejiang Province [LR18B020001]
  3. Fundamental Research Funds for the Central Universities [2019FZA3007]
  4. TopNotch Young Talents Program of China

向作者/读者索取更多资源

A tetrahedral radical cage was synthesized via condensation reaction, showing homochirality confirmed by X-ray crystallography. The homochirality in the cage framework resulted from [CH...pi] and hydrogen-bonding interactions. The cage contained four PTM radicals with weak through-space coupling, each bearing 3.58 spins as demonstrated by magnetic measurements.
Condensation of an inherently C-3-symmetric polychlorotriphenylmethyl (PTM) radical trisaldehyde with tris(2-aminoethyl)amine (TREN) yields a [4+4] tetrahedral radical cage as a racemic pair of homochiral enantiomers in 75 % isolated yield. The structure was characterized by X-ray crystallography, confirming the homochirality of each cage framework. The homochirality results from intramolecular [CH...pi] and hydrogen-bonding interactions within the cage framework. The four PTM radicals in a cage undergo weak through-space coupling. Magnetic measurements demonstrated that each cage bears 3.58 spins.

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