Radical cyclopolymerization of 3-phenyl[5]
ferrocenophane-1,5-dimethylene (2) and copolymerization with styrene gave polymers (3 and 4) with [3]ferrocenophane moieties pendant to the backbone. Cyclic voltammetry (CV) on polymer 3 in CH 2 Cl 2 showed two oxidation waves at 00.13 and /0.05 V (versus ferrocene/ferrocenium) and CV on copolymer 4 showed one oxidation potential at 00.03 V. CV on 3 in dimethylacetamide showed only one oxidation potential at 00.10 V. Near-IR spectroscopy of partially oxidized 3 showed a broad intervalence band at ca. 2000 nm, indicative of low-energy barriers to electron hopping. Conductivity measurements on 3 and poly-(vinylferrocene) (PVFc) oxidatively doped with iodine vapors under an argon atmosphere showed a maximum conductivity ca. 5 1 10 05 S/cm before the samples cracked, while 4 exhibited a maximum conductivity of 1.6 1 10 06 S/cm. On iodine doping under ambient conditions, polymers 3, 4, and PVFc showed maximum conductivities of 7.6 1 10 04 , 9.5 1 10 05 , and 5.5 1 10 05 S/cm, respectively. Conductivity measurement were also performed on samples of 3 / BF 0 4 with oxidation levels ranging from 8 to 56%. Conductivities of these samples ranged from ca. 10 010 to 10 09 S/cm under vacuum and ca. 10 06 S/cm under ambient conditions, indicating that atmospheric moisture has a strong effect on the conductivity.