Synthesis of aromatic polynitroso compounds: Towards functional azodioxy-linked porous polymers

Abstract

The polymerization property of aromatic polynitroso compounds could be used to create azodioxy porous networks with possible application for the adsorption of CO2, the main greenhouse gas. Herein, we report the synthesis and characterization of new aromatic polynitroso compounds, with para-nitroso groups attached to the triphenylbenzene, triphenylpyridine, triphenyltriazine and triphenylamine moiety. The synthesis of the pyridine-based trinitroso compound was performed by reduction of the corresponding trinitro derivative to N-arylhydroxylamine followed by oxidation to the trinitroso product. For the synthesis of the benzene- and triazine-based trinitroso compounds, a novel synthetic strategy was implemented, which included cyclotrimerization of the 4-nitrosoacetophenone and 4-nitrosobenzonitrile, respectively. Reduction of the trinitro compound with triphenylamine unit produced the dinitroso product. In a solid state, all synthesized compounds form E-azodioxy oligomers or polymers. While azodioxy polymer with triphenylbenzene moiety is an amorphous solid, other azodioxy oligomers and polymers displayed sharp diffraction peaks pointing to their crystalline nature. A computational study indicated that eclipsed AA configurations are preferred over staggered AB and inclined AA’ configurations. The serrated layers may be the most likely outcome when/if 2D layers form an organized polymer network of azodioxy linked triphenyltriazine-based building blocks.