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説明:

Implementing chemical reactivity into synthetic supramolecular polymers based on π-conjugated molecules has been of great interest to create functional materials with spatiotemporal dynamic properties. However, the development of in situ chemical reaction within supramolecular polymers is still in its infancy, because one needs to design an optimal π-conjugated monomers having excellent reactivity under mild conditions possibly without byproducts or a catalyst. Herein we report the synthesis of a supramolecular polymer based on ethynyl core-substituted naphthalenediimide (S-NDI2) molecules that react with various amines quantitatively in nonpolar solvent, without a catalyst, at 298 K. Most interestingly, the in situ reaction of the S-NDI2 supramolecular polymer with a linear aliphatic diamine proceeded much faster than the homogeneous reaction of a monomeric naphthalenediimide with the same diamine, affording diamine-linked S-NDI2 oligomers and polymers. The acceleration of the in situ hydroamination was presumably due to rapid intra-supramolecular cross-linking between ethynyl and amino groups fixed in close proximity within the supramolecular polymer. Such intra-supramolecular cross-linking did not occur efficiently with an incompatible diamine. The systematic kinetic studies of in situ catalyst-free hydroamination within supramolecular polymers provide us with a useful, facile and versatile tool kit for designing dynamic supramolecular polymeric materials based on electron-deficient π-conjugated monomers.

権利情報:

• cc-by-nc-3.0
  

キーワード: Supramolecular polymers, Hydroamination, Catalyst-free click reaction, Naphthalenediimide (NDI), Reaction dynamics

刊行年月日: 2022-03-23

出版者: Royal Society of Chemistry (RSC)

掲載誌:

• Chemical Science (ISSN: 20416520) p. 4413-4423

研究助成金:

• Murata Science Foundation
• Ministry of Education, Culture, Sports, Science and Technology 20H05868
• Japan Society for the Promotion of Science 19K0564

原稿種別: 出版者版 (Version of record)

MDR DOI:

公開URL: https://doi.org/10.1039/d2sc00035k

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更新時刻: 2025-08-23 08:30:36 +0900

MDRでの公開時刻: 2025-08-23 08:17:04 +0900