Reactivity of NO 2 with Porous and Conductive Copper Azobispyridine Metallopolymers

We report the reactivity of copper azobispyridine (abpy) metallopolymers with nitrogen dioxide (NO ). The porous and conductive [Cu(abpy)] mixed-valence metallopolymers undergo a redox reaction with NO , resulting in the disproportionation of NO gas. Solid- and gas-phase vibrational spectroscopy and X-ray analysis of the reaction products of the NO -dosed metallopolymer show evidence of nitrate ions and nitric oxide gas. Exposure to NO results in complete loss of porosity and a decrease in the room-temperature conductivity of the metallopolymer by four orders of magnitude with the loss of mixed-valence character. Notably, the porous and conductive [Cu(abpy)] metallopolymers can be reformed by reducing the Cu-nitrate species.