Clayman Naomi E, Manumpil Mary Anne, Matson Benjamin D, Wang Shengkai, Slavney Adam H, Sarangi Ritimuka, Karunadasa Hemamala I, Waymouth Robert M
Department of Chemistry , Stanford University , Stanford , California 94305 , United States.
Stanford Synchrotron Radiation Lightsource , SLAC National Accelerator Laboratory , Menlo Park , California 94025 , United States.
Inorg Chem. 2019 Aug 19;58(16):10856-10860. doi: 10.1021/acs.inorgchem.9b01190. Epub 2019 Jul 31.
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.
我们报道了偶氮双吡啶铜（abpy）金属聚合物与二氧化氮（NO）的反应活性。多孔导电的[Cu(abpy)]混合价金属聚合物与NO发生氧化还原反应，导致NO气体歧化。对用NO处理过的金属聚合物的反应产物进行的固相和气相振动光谱以及X射线分析表明存在硝酸根离子和一氧化氮气体。暴露于NO会导致孔隙率完全丧失，并且金属聚合物的室温电导率随着混合价特性的丧失而降低四个数量级。值得注意的是，通过还原硝酸铜物种，多孔导电的[Cu(abpy)]金属聚合物可以重新形成。
