Carving Out Pores in Redox‐Active One‐Dimensional Coordination Polymers

Reduction of the insulating one‐dimensional coordination polymer [Cu(abpy)PF 6 ] n , 1 a (PF 6 ), (abpy=2,2′‐azobispyridine) yields the conductive, porous polymer [Cu(abpy)] n , 2 a . Pressed pellets of neutral 2 a exhibit a conductivity of 0.093 S cm −1 at room temperature and a Brunauer–Emmett–Teller (BET) surface area of 56 m 2  g −1 . Fine powders of 2 a have a BET surface area of 90 m 2  g −1 . Cyclic voltammetry shows that the reduction of 1 a (PF 6 ) to 2 a is quasi‐reversible, indicative of facile charge transfer through the bulk material. The BET surface area of the reduced polymer 2 can be controlled by changing the size of the counteranion X in the cationic [Cu(abpy)X] n . Reduction of [Cu(abpy)X] n with X=Br ( 2 b ) or BAr F ( 2 c ; BAr F =tetrakis(3,5‐bis(trifluoromethyl)phenyl)), affords [Cu(abpy)] n polymers with surface areas of 60 and 200 m 2  g −1 , respectively.