Two-dimensionally extended aromatic polyamines for optimization of charge-transporting properties by partial oxidation

Tsuyoshi Michinobu, Fumiaki Kato, J. U N Inui, Hiroyuki Nishide

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

This article describes the synthesis of the two-dimensionally extended aromatic polyamines by polycondensation between the tri-sec-amine monomer and pphenylenediamine-based dibromide, the polyradical generation by chemical and electrochemical oxidations, and the hole-transporting properties. The molecular weights (Mn) of the polyamines, 3a and 3b, were 7700 and 5000, respectively, and both polymers were very soluble in the typical organic solvents, ensuring a good film formation capability by a spin-coating technique. The thermal stability of the aromatic polyamines, elucidated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), was quite high. More important, the cross-conjugated structure is essential for the controlled radical generation and the maintenance of the radical stability. Cyclic voltammograms of the neutral polyamines in the presence of 1 vol % of trifluoroacetic acid and the intervalence bands of the partially oxidized polyamines with NOPF6 revealed that the generated radicals delocalize over the p-phenylenediamine moieties. The half-life of the polyradicals was about 12 h even under ambient conditions, which allowed us to fabricate and measure the hole-only devices. The charge-transporting properties of the polyamines were dramatically changed by the partial oxidation (20 mol %/aminium unit) with NOPF6. The neutral polyamines showed the conventional injection-limit behaviors, whereas the hole-transporting behaviors of the polyradicals are bulk-limit and highly dependent on the chemical structure. The efficient hole-transport of the all-conjugated poly(aminium cationic radicaDs was for the first time realized for the polyradical of 3b.

Original languageEnglish
Pages (from-to)4577-4586
Number of pages10
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume47
Issue number18
DOIs
Publication statusPublished - 2009 Sep 15

Fingerprint

Polyamines
Oxidation
Trifluoroacetic acid
Trifluoroacetic Acid
Coating techniques
Electrochemical oxidation
Spin coating
Polycondensation
Organic solvents
Amines
Thermogravimetric analysis
Differential scanning calorimetry
Polymers
Thermodynamic stability
Monomers
Molecular weight

Keywords

  • Charge transport
  • Conjugated polymers
  • Electrochemistry
  • Polyamines
  • Polycondensation

ASJC Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics
  • Organic Chemistry

Cite this

Two-dimensionally extended aromatic polyamines for optimization of charge-transporting properties by partial oxidation. / Michinobu, Tsuyoshi; Kato, Fumiaki; Inui, J. U N; Nishide, Hiroyuki.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 47, No. 18, 15.09.2009, p. 4577-4586.

Research output: Contribution to journalArticle

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