Ladder oligo(m -aniline)s

Derivatives of azaacenes with cross-conjugated π-systems

Andrzej Rajca, Przemysław J. Boratyński, Arnon Olankitwanit, Kouichi Shiraishi, Maren Pink, Suchada Rajca

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

We describe the synthesis and electronic properties of ladder oligomers of poly(m-aniline) that may be considered as derivatives of azaacenes with cross-conjugated π-systems. Syntheses of ladder oligo(m-aniline)s with 9 and 13 collinearly fused six-membered rings employed Pd-catalyzed aminations and Friedel-Crafts-based ring closures. Structures were confirmed by either X-ray crystallography or correlations between DFT-computed and experimental spectroscopic data such as 1H, 13C, and 15N NMR chemical shifts and electronic absorption spectra. All compounds have planar "azaacene" moieties. The experimental band gaps E g ≈ 3.5-3.65 eV, determined by the UV-vis absorption onsets, were in agreement with the TD-DFT-computed vertical excitation energies to the S 1 state. Fluorescence quantum yields of up to 20% were found. Electrochemically estimated HOMO energies of -4.8 eV suggested propensity for a facile one-electron oxidation and just sufficient environmental stability toward oxygen (O 2). For two oligomers with "tetraazanonacene" moieties, potentials of E 4+/3+ ≈ 1.6-1.7 V vs SCE were determined for four-electron oxidation to the corresponding tetraradical tetracations.

Original languageEnglish (US)
Pages (from-to)2107-2120
Number of pages14
JournalJournal of Organic Chemistry
Volume77
Issue number5
DOIs
StatePublished - Mar 2 2012

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Ladders
Oligomers
Discrete Fourier transforms
Derivatives
Amination
Oxidation
Electrons
Excitation energy
X ray crystallography
Chemical shift
Quantum yield
Electronic properties
Absorption spectra
Energy gap
Fluorescence
Nuclear magnetic resonance
Oxygen
aniline

ASJC Scopus subject areas

  • Organic Chemistry

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Ladder oligo(m -aniline)s : Derivatives of azaacenes with cross-conjugated π-systems. / Rajca, Andrzej; Boratyński, Przemysław J.; Olankitwanit, Arnon; Shiraishi, Kouichi; Pink, Maren; Rajca, Suchada.

In: Journal of Organic Chemistry, Vol. 77, No. 5, 02.03.2012, p. 2107-2120.

Research output: Contribution to journalArticle

Rajca, Andrzej ; Boratyński, Przemysław J. ; Olankitwanit, Arnon ; Shiraishi, Kouichi ; Pink, Maren ; Rajca, Suchada. / Ladder oligo(m -aniline)s : Derivatives of azaacenes with cross-conjugated π-systems. In: Journal of Organic Chemistry. 2012 ; Vol. 77, No. 5. pp. 2107-2120.
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