title: Conducting metallopolymers based on azaferrocene.
abstract: A series of 2,5-thiophene-substituted 1',2',3',4',5'-pentamethylazaferrocene complexes were synthesized and electropolymerized to produce polymers with fully pi-conjugated backbones. The length and hence oxidation potential of the conjugated linker (the thiophene fragments) between the metal centers were varied to understand the influence of the metal-metal interactions on the overall electroactivity of the resulting polymer. These complexes were electrochemically polymerized, and the resulting polymers were characterized by cyclic voltammetry, in situ conductivity, and spectroelectrochemistry measurements. The iron-centered oxidations significantly increased the conductivity of the polymer. The results reveal that shorter conjugated linkers cause the onset of conductivity to occur at lower potentials. This effect implies that a superexchange mechanism is likely operative in the charge migration of these polymers.
authors.affiliation: Institute for Soldier Nanotechnologies and Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
authors.forename: Paul D
authors.initials: PD
authors.lastname: Byrne
authors.forename: Peter
authors.initials: P
authors.lastname: Müller
authors.forename: Timothy M
authors.initials: TM
authors.lastname: Swager
mesh_terms: D001372:Aza Compounds / Q000737:chemistry*; D004553:Electric Conductivity; D005296:Ferrous Compounds / Q000737:chemistry*; D000075163:Metallocenes; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D001372:Aza Compounds; D005296:Ferrous Compounds; D000075163:Metallocenes; D009942:Organometallic Compounds; D011108:Polymers; C004998:ferrocene