Carving Out Pores in Redox-Active One-Dimensional Coordination Polymers
Naomi E. Clayman
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
These authors contributed equally to this work.
Search for more papers by this authorMary Anne Manumpil
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
These authors contributed equally to this work.
Search for more papers by this authorDaiki Umeyama
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Present Address: International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044 Japan
Search for more papers by this authorAndrey E. Rudenko
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorCorresponding Author
Hemamala I. Karunadasa
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorCorresponding Author
Robert M. Waymouth
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorNaomi E. Clayman
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
These authors contributed equally to this work.
Search for more papers by this authorMary Anne Manumpil
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
These authors contributed equally to this work.
Search for more papers by this authorDaiki Umeyama
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Present Address: International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044 Japan
Search for more papers by this authorAndrey E. Rudenko
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorCorresponding Author
Hemamala I. Karunadasa
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorCorresponding Author
Robert M. Waymouth
Department of Chemistry, Stanford University, Stanford, CA, 94305 USA
Search for more papers by this authorGraphical Abstract
Templating pores in polymers: Reduction of non-porous cationic insulating coordination polymers (see picture, left) yields porous neutral conductive polymers (right). The porosity varies with the size of the anion that departs the parent polymer.
Abstract
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.
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