Supramolecular helix-helix block copolymers

Anna Croom, Kylie B. Manning, Marcus Weck

Research output: Contribution to journalArticle

Abstract

Two chemically distinct monotelechelic helical polymers were synthesized using anionic and reversible addition-fragmentation chain-transfer (RAFT) polymerizations. A chiral poly(isocyanide) block was obtained using a palladium-ethynyl complex modified with the N1,N3-bis(6-butyramidopyridin-2-yl)-5-hydroxyisophthalamide (Hamilton wedge) moiety as a catalyst employing anionic polymerization. A complementary barbiturate-functionalized chain-transfer agent was used to polymerize chiral N-(1-(naphthalen-2-yl)ethyl)methacrylamides by RAFT polymerization. The assembly into helix-helix supramolecular block copolymers in chloroform via hydrogen bonding was analyzed by 1H NMR spectroscopy, resulting in an average measured association constant of (9.5 ± 0.5) × 103 M-1. After block copolymer formation, the secondary structures of both helical polymers were maintained within the block copolymer, as evidenced by circular dichroism and infrared spectroscopies. Films were prepared from a 1:1 mixture of polymers in solution and were analyzed by WAXS and DSC to evaluate organization in the solid state. While diblock formation in the solution phase is readily obtainable, there was little evidence supporting a self-assembly assisted microstructure in the solid state. This work demonstrates a synthetic methodology for obtaining two telechelic helical polymers capable of supramolecular assembly in solution toward the goals of developing multifunctional polymeric ensembles.

Original languageEnglish (US)
Pages (from-to)7117-7128
Number of pages12
JournalMacromolecules
Volume49
Issue number19
DOIs
StatePublished - Oct 11 2016

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Block copolymers
Polymers
Polymerization
Circular dichroism spectroscopy
Anionic polymerization
Palladium
Cyanides
Chloroform
Chlorine compounds
Self assembly
Nuclear magnetic resonance spectroscopy
Infrared spectroscopy
Hydrogen bonds
Association reactions
Microstructure
Catalysts

ASJC Scopus subject areas

  • Organic Chemistry
  • Materials Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry

Cite this

Supramolecular helix-helix block copolymers. / Croom, Anna; Manning, Kylie B.; Weck, Marcus.

In: Macromolecules, Vol. 49, No. 19, 11.10.2016, p. 7117-7128.

Research output: Contribution to journalArticle

Croom, Anna ; Manning, Kylie B. ; Weck, Marcus. / Supramolecular helix-helix block copolymers. In: Macromolecules. 2016 ; Vol. 49, No. 19. pp. 7117-7128.
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