Rate-determining factors in the chain polymerization of molecules initiated by local single-molecule excitation

Swapan K. Mandal, Yuji Okawa, Tsuyoshi Hasegawa, Masakazu Aono

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

Spontaneous chain polymerization of molecules initiated by a scanning tunneling microscope tip is studied with a focus on its rate-determining factors. Such chain polymerization that happens in self-assembled monolayers (SAM) of diacetylene compound molecules, which results in a π-conjugated linear polydiacetylene nanowire, varies in its rate P depending on domains in the SAM and substrate materials. While the arrangement of diacetylene molecules is identical in every domain on a graphite substrate, it varies in different domains on a MoS2 substrate. This structural variation enables us to investigate how P is affected by molecular geometry. An important determining factor of P is the distance between two carbon atoms which are to be bound by polymerization reaction, R; as R decreases by 0.1 nm, P increases ∼2 times. P for a MoS2 substrate is ∼4 times higher (with the same value of R) than that for a graphite substrate because of higher mobility of molecules. The exciting correlation of the chain polymerization rate to the geometrical structure of the diacetylene molecules brings a deeper understanding of the mechanism of chain polymerization kinetics. In addition, the fabrication of one-dimensional conjugated polymer nanowires on a semiconducting MoS2 substrate as demonstrated here may be of immense importance in the realization of future molecular devices.

Original languageEnglish
Pages (from-to)2779-2786
Number of pages8
JournalACS Nano
Volume5
Issue number4
DOIs
Publication statusPublished - 2011 Apr 26
Externally publishedYes

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polymerization
Polymerization
Molecules
Substrates
excitation
molecules
Graphite
Self assembled monolayers
Nanowires
nanowires
graphite
Conjugated polymers
Microscopes
Carbon
microscopes
Scanning
Fabrication
Atoms
fabrication
Kinetics

Keywords

  • chain polymerization rate
  • molybdenum disulfide
  • polydiacetylene
  • polymer nanowire
  • scanning tunneling microscopy

ASJC Scopus subject areas

  • Engineering(all)
  • Materials Science(all)
  • Physics and Astronomy(all)

Cite this

Rate-determining factors in the chain polymerization of molecules initiated by local single-molecule excitation. / Mandal, Swapan K.; Okawa, Yuji; Hasegawa, Tsuyoshi; Aono, Masakazu.

In: ACS Nano, Vol. 5, No. 4, 26.04.2011, p. 2779-2786.

Research output: Contribution to journalArticle

Mandal, Swapan K. ; Okawa, Yuji ; Hasegawa, Tsuyoshi ; Aono, Masakazu. / Rate-determining factors in the chain polymerization of molecules initiated by local single-molecule excitation. In: ACS Nano. 2011 ; Vol. 5, No. 4. pp. 2779-2786.
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