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

Reduction of the insulating one-dimensional coordination polymer [Cu(abpy)PF6 ]n , 1 a(PF6 ), (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 m2  g-1 . Fine powders of 2 a have a BET surface area of 90 m2  g-1 . Cyclic voltammetry shows that the reduction of 1 a(PF6 ) 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 BArF (2 c; BArF =tetrakis(3,5-bis(trifluoromethyl)phenyl)), affords [Cu(abpy)]n polymers with surface areas of 60 and 200 m2  g-1 , respectively.