Supramolecular ABC triblock copolymers via one-pot, orthogonal self-assembly

Si Kyung Yang, Ashootosh V. Ambade, Marcus Weck

Research output: Contribution to journalArticle

Abstract

A heterotelechelic poly(norbornene imide) containing two terminal and orthogonal hydrogen-bonding receptors, N,N′-bis[6-(alkanoylamino)pyridin- 2-yl] isophthalamide (often referred to as the Hamilton receptor or Wedge) and 2,7-diamido-1,8-naphthyridine (DAN), at the opposite ends of the polymer was synthesized via ring-opening metathesis polymerization (ROMP) through the employment of a Hamilton receptor-functionalized ruthenium initiator and a DAN-based chain-terminator. In parallel, two monotelechelic polymers containing either cyanuric acid (CA)- or ureidoguanosine (UG)-end groups that are complementary to the hydrogen-bonding receptors along the poly(norbornene imide) were synthesized either also via ROMP by terminating the polymerization of norbornene octyl ester with a CA-based chain-terminator or by the reaction of poly(ethylene oxide) with UG. Complete incorporations of the hydrogen-bonding receptors at the chain-ends of all polymers were confirmed by 1H NMR spectroscopy. The telechelic polymers can be self-assembled into ABC triblock copolymers following either a stepwise or a one-pot, orthogonal self-assembly protocol. The self-assembly process was monitored by 1H NMR spectroscopy, revealing full orthogonality of the two recognition pairs, Hamilton receptor-CA and DAN-UG. The resulting supramolecular ABC triblock copolymers were further characterized by a series of methods including 2-D NOESY, isothermal titration calorimetry, and viscometry, proving that the two orthogonal hydrogen-bonding interactions are strong enough to hold the three polymer chains together. We suggest that a self-assembly methodology solely based on the fully orthogonal hydrogen-bonding recognition motifs will allow for an easy and rapid synthesis of architecturally controlled supramolecular polymeric assemblies with a high degree of complexity.

Original languageEnglish (US)
Pages (from-to)1637-1645
Number of pages9
JournalJournal of the American Chemical Society
Volume132
Issue number5
DOIs
StatePublished - Feb 10 2010

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Hydrogen Bonding
Self assembly
Block copolymers
Hydrogen bonds
Polymers
Naphthyridines
Polymerization
Imides
Ring opening polymerization
Nuclear magnetic resonance spectroscopy
Acids
Magnetic Resonance Spectroscopy
Ethylene Oxide
Calorimetry
Ruthenium
Viscosity measurement
Polyethylene oxides
Titration
Esters
cyanuric acid

ASJC Scopus subject areas

  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry
  • Chemistry(all)

Cite this

Supramolecular ABC triblock copolymers via one-pot, orthogonal self-assembly. / Yang, Si Kyung; Ambade, Ashootosh V.; Weck, Marcus.

In: Journal of the American Chemical Society, Vol. 132, No. 5, 10.02.2010, p. 1637-1645.

Research output: Contribution to journalArticle

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