Ladder oligo(m-aniline)s: derivatives of azaacenes with cross-conjugated π-systems

The Journal of Organic Chemistry
Andrzej RajcaSuchada Rajca

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 (1)H, (13)C, and (15)N 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.

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Citations

Mar 28, 2017·The Journal of Physical Chemistry. B·Lukasz SkorkaIrena Kulszewicz-Bajer
Jan 13, 2015·The Journal of Organic Chemistry·Nolan M GallagherAndrzej Rajca
Sep 14, 2013·Chemical Society Reviews·Piotr BujakAdam Pron
Oct 17, 2014·Physical Chemistry Chemical Physics : PCCP·Svante HedströmPetter Persson
Feb 28, 2013·Organic & Biomolecular Chemistry·Koji TakagiMasanori Sakaida
Aug 10, 2012·The Journal of Organic Chemistry·Shin-ichiro KatoYosuke Nakamura
Jan 8, 2013·Journal of Chemical Theory and Computation·Vincenzo BaroneGiacomo Prampolini
Nov 21, 2013·Journal of the American Chemical Society·Andrzej RajcaSuchada Rajca
Apr 9, 2013·Journal of Chemical Theory and Computation·Vincenzo BaroneGiacomo Prampolini
Apr 23, 2015·The Journal of Organic Chemistry·Arnon OlankitwanitAndrzej Rajca
Sep 14, 2014·Journal of the American Chemical Society·Arnon OlankitwanitAndrzej Rajca
Jun 2, 2012·Organic Letters·Makoto MiyasakaAndrzej Rajca

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