Synthesis and spectroscopic characterization of polymer and oligomers of ortho-phenylenediamine

Poly(ortho-phenylenediamine) and oligomers of ortho-phenylenediamine were chemically synthesized and characterized by UV-vis, (1)H and (13)C NMR, FTIR and resonance Raman spectroscopies. Polymerization of ortho-phenylenediamine in HCl medium with ammonium persulfate only leads the trimer compound, in disagreement with some previous reports. Nevertheless, in acetic acid medium it was possible to prepare a polymer constituted by ladder phenazinic segments with different protonation levels and quinonediimine rings (polyaniline-like). X-ray absorption at N K-edge (N K XANES), X-ray photoelectron (XPS) and Electron paramagnetic resonance (EPR) spectroscopies were used to determine the different kinds of nitrogen presents in this class of polymer. N K XANES spectrum of poly(ortho-phenylenediamine) shows the band of -N=nitrogen of non-protonated phenazinic rings at 398.2 eV. In addition, XPS and N K XANES data confirm the presence of different types of protonated nitrogens in the polymeric poly(ortho-phenylenediamine) chain and the EPR spectrum shows that the polymer has a very weak polaronic signal. (C) 2009 Elsevier Ltd. All rights reserved.

FAPESP (Brazilian agency)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

CNPq

National Synchrotron Light Laboratory (LNLS/Brazil)

National Synchrotron Light Laboratory (LNLS/Brazil)[1026/01]

National Synchrotron Light Laboratory (LNLS/Brazil)[1427/02]

National Synchrotron Light Laboratory (LNLS/Brazil)

National Synchrotron Light Laboratory (LNLS/Brazil)

National Synchrotron Light Laboratory (LNLS/Brazil)[1432/02]

National Synchrotron Light Laboratory (LNLS/Brazil)[2169/03]

National Synchrotron Light Laboratory (LNLS/Brazil)