| Abstract: | 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 CH2Cl2 showed two oxidation waves at −0.13 and +0.05 V (versus ferrocene/ferrocenium) and CV on copolymer 4 showed one oxidation potential at −0.03 V. CV on 3 in dimethylacetamide showed only one oxidation potential at −0.10 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 × 10−5 S/cm before the samples cracked, while 4 exhibited a maximum conductivity of 1.6 × 10−6 S/cm. On iodine doping under ambient conditions, polymers 3 , 4 , and PVFc showed maximum conductivities of 7.6 × 10−4, 9.5 × 10−5, and 5.5 × 10−5 S/cm, respectively. Conductivity measurement were also performed on samples of 3 +BF4− with oxidation levels ranging from 8 to 56%. Conductivities of these samples ranged from ca. 10−10 to 10−9 S/cm under vacuum and ca. 10−6 S/cm under ambient conditions, indicating that atmospheric moisture has a strong effect on the conductivity. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3365–3376, 1997 |
