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Selective synthesis of tightly- and loosely-twisted metallomacrocycle isomers towards precise control of helicity inversion motion

Author

Listed:
  • Tomoki Nakajima

    (The University of Tokyo)

  • Shohei Tashiro

    (The University of Tokyo)

  • Masahiro Ehara

    (Institute for Molecular Science, Myodaiji)

  • Mitsuhiko Shionoya

    (The University of Tokyo)

Abstract

Molecular twist is a characteristic component of molecular machines. Selectively synthesising isomers with different modes of twisting and controlling their motion such as helicity inversion is an essential challenge for achieving more advanced molecular systems. Here we report a strategy to control the inversion kinetics: the kinetically selective synthesis of tightly- and loosely-twisted isomers of a trinuclear PdII-macrocycle and their markedly different molecular behaviours. The loosely-twisted isomers smoothly invert between (P)- and (M)-helicity at a rate of 3.31 s–1, while the helicity inversion of the tightly-twisted isomers is undetectable but rather relaxes to the loosely-twisted isomers. This critical difference between these two isomers is explained by the presence or absence of an absolute configuration inversion of the nitrogen atoms of the macrocyclic amine ligand. Strategies to control the helicity inversion and structural loosening motions by the mode of twisting offer future possibilities for the design of molecular machines.

Suggested Citation

  • Tomoki Nakajima & Shohei Tashiro & Masahiro Ehara & Mitsuhiko Shionoya, 2023. "Selective synthesis of tightly- and loosely-twisted metallomacrocycle isomers towards precise control of helicity inversion motion," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-43658-5
    DOI: 10.1038/s41467-023-43658-5
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    References listed on IDEAS

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