Bifurcation of self-assembly pathways to sheet or cage controlled by kinetic template effect

Leonardo Hayato Foianesi-Takeshige, Satoshi Takahashi, Tomoki Tateishi, Ryosuke Sekine, Atsushi Okazawa, Wenchao Zhu, Tatsuo Kojima, Koji Harano, Eiichi Nakamura, Hirofumi Sato, Shuichi Hiraoka*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)

Abstract

The template effect is a key feature to control the arrangement of building blocks in assemblies, but its kinetic nature remains elusive compared to the thermodynamic aspects, with the exception of very simple reactions. Here we report a kinetic template effect in a self-assembled cage composed of flexible ditopic ligands and Pd(II) ions. Without template anion, a micrometer-sized sheet is kinetically trapped (off-pathway), which is converted into the thermodynamically most stable cage by the template anion. When the template anion is present from the start, the cage is selectively produced by the preferential cyclization of a dinuclear intermediate (on-pathway). Quantitative and numerical analyses of the self-assembly of the cage on the on-pathway revealed that the accelerating effect of the template is stronger for the early stage reactions of the self-assembly than for the final cage formation step itself, indicating the kinetic template effect.

Original languageEnglish
Article number128
JournalCommunications Chemistry
Volume2
Issue number1
DOIs
Publication statusPublished - 2019 Dec 1
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Chemistry
  • Environmental Chemistry
  • Biochemistry

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