Jump to main content
Jump to site search


A versatile synthetic strategy for macromolecular cages: intramolecular consecutive cyclization of star-shaped polymers

Author affiliations

Abstract

Cage-shaped polymers, or “macromolecular cages”, are of great interest as the macromolecular analogues of molecular cages because of their various potential applications in supramolecular chemistry and materials science. However, the systematic synthesis of macromolecular cages remains a great challenge. Herein, we describe a robust and versatile synthetic strategy for macromolecular cages with defined arm numbers and sizes based on the intramolecular consecutive cyclization of highly reactive norbornene groups attached to each end of the arms of a star-shaped polymer precursor. The cyclizations of three-, four-, six-, and eight-armed star-shaped poly(ε-caprolactone)s (PCLs) bearing a norbornenyl group at each arm terminus were effected with Grubbs' third generation catalyst at high dilution. 1H NMR, SEC, and MALDI-TOF MS analyses revealed that the reaction proceeded to produce the desired macromolecular cages with sufficient purity. The molecular sizes of the macromolecular cages were controlled by simply changing the molecular weight of the star-shaped polymer precursors. Systematic investigation of the structure–property relationships confirmed that the macromolecular cages adopt a much more compact conformation, in both the solution and bulk states, as compared to their linear and star-shaped counterparts. This synthetic approach marks a significant advance in the synthesis of complex macromolecular architectures and provides a platform for novel applications using cage-shaped molecules with polymer frameworks.

Graphical abstract: A versatile synthetic strategy for macromolecular cages: intramolecular consecutive cyclization of star-shaped polymers

Back to tab navigation

Supplementary files

Publication details

The article was received on 10 Sep 2018, accepted on 10 Oct 2018 and first published on 11 Oct 2018


Article type: Edge Article
DOI: 10.1039/C8SC04006K
Citation: Chem. Sci., 2019, Advance Article
  • Open access: Creative Commons BY license
  •   Request permissions

    A versatile synthetic strategy for macromolecular cages: intramolecular consecutive cyclization of star-shaped polymers

    Y. Mato, K. Honda, K. Tajima, T. Yamamoto, T. Isono and T. Satoh, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C8SC04006K

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements