Copolymerization of terephthalaldehyde with pyrrole, indole and carbazole gives microporous POFs functionalized with unpaired electrons

Alexandros P. Katsoulidis, Scott M. Dyar, Raanan Carmieli, Christos D. Malliakas, Michael R Wasielewski, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

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Abstract

A new family of paramagnetic microporous polymeric organic frameworks (POFs) has been developed through the co-polymerization of terephthalaldehyde and pyrrole, indole, and carbazole, respectively. These POFs are functionalized with stable unpaired electrons and electron paramagnetic resonance spectroscopy and pulsed ENDOR spectroscopy confirms their existence. The free radicals are produced in the early steps of polymerization and are responsible for their optical properties and the chemical adsorption properties of the POFs. The optical band gap of these materials ranges from 0.8 to 1.6 eV. The new POFs have spherical morphology and exhibit surface areas up to 777 m2 g -1 (Pyr-POF-1). Furthermore, Pyr-POF-1 displays the uptake of CO 2 14% wt and C2H6 9% wt at 273 K/1 bar and H2 1.2% wt at 77 K/1 bar. The pyrrole based material (Pyr-POF-2) shows high capacity for CO2, 10% wt, under ambient conditions (298 K/1 bar) and the isosteric heat of CO2 adsorption of ∼34 kJ mol-1. The preparation of this new POF family is based on a very simple synthetic pathway and highlights the significance of terephthalaldehyde as a precursor for the synthesis of low cost functional porous polymers.

Original languageEnglish
Pages (from-to)10465-10473
Number of pages9
JournalJournal of Materials Chemistry A
Volume1
Issue number35
DOIs
Publication statusPublished - Sep 21 2013

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Pyrroles
Copolymerization
Electrons
Spectroscopy
Adsorption
Optical band gaps
Polymers
Carbon Monoxide
Free radicals
Free Radicals
Paramagnetic resonance
Optical properties
Display devices
Polymerization
carbazole
indole

ASJC Scopus subject areas

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

Cite this

Copolymerization of terephthalaldehyde with pyrrole, indole and carbazole gives microporous POFs functionalized with unpaired electrons. / Katsoulidis, Alexandros P.; Dyar, Scott M.; Carmieli, Raanan; Malliakas, Christos D.; Wasielewski, Michael R; Kanatzidis, Mercouri G.

In: Journal of Materials Chemistry A, Vol. 1, No. 35, 21.09.2013, p. 10465-10473.

Research output: Contribution to journalArticle

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