Shape-directed assembly of a "macromolecular barb" into nanofibers: Stereospecific cyclopolymeriztion of isopropylidene diallylmalonate

Yasunao Miyamura, Kazushi Kinbara, Yohei Yamamoto, Vakayil K. Praveen, Kenichi Kato, Masaki Takata, Takano Atsushi, Yushu Matsushita, Eunjl Lee, Myongsoo Lee, Takuzo Aida

Research output: Contribution to journalArticlepeer-review

30 Citations (Scopus)

Abstract

(Figure Presented) Cyclopolymerization of isopropylidene diallylmalonate (1) in CH2Cl2 using as the initiator a crystallographically defined α-diimine Pd(II) complex with a trans-azobenzene strap (trans-3) proceeds stereospecifically to give a cycloolefinic polymer that is rich in threo-disyndiotactic sequences (strich-2; syndiotactic tetrad content = 60% at -10 to 0 °C). Polymer 2, when perfectly threo-disyndiotactic, adopts a "barb"-shaped geometry with its cyclic malonate pendants sticking out alternately up and down along the rigid main chain. Under appropriate conditions, strich-2 regularly self-assembles, not only in the solid state but also in solution, into nanofibers that eventually give rise to physical gelation of halogenated solvents such as CH2Cl 2. In sharp contrast, a reference polymer 2 that is rich in threo-diisotactic sequences (itrich-2), which likely adopts a helical geometry, has poor self-assembly capability in solution and neither forms nanofibers nor induces physical gelation of CH2Cl2.

Original languageEnglish
Pages (from-to)3292-3294
Number of pages3
JournalJournal of the American Chemical Society
Volume132
Issue number10
DOIs
Publication statusPublished - 2010 Mar 17

ASJC Scopus subject areas

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

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