Journal of Polymer Science Part A: Polymer Chemistry, Vol.35, No.16, 3365-3376, 1997
Cyclopolymerization of 3-Phenyl(5)Ferrocenophane-1,5-Dimethylene - Synthesis and Electronic-Properties of a Polyferrocenophane
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 X 10(-5) S/cm before the samples cracked, while 4 exhibited a maximum conductivity of 1.6 x 10(-6) S/cm. On iodine doping under ambient conditions, polymers 3, 4, and PVFc showed maximum conductivities of 7.6 x 10(-4), 9.5 x 10(-5), and 5.5 x 10(-5) S/cm, respectively. Conductivity measurement were also performed on samples of 3(+)BF(4)(-) 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.
Keywords:RING-OPENING POLYMERIZATION;POLYMERS;POLY((E;E)-(6.2)PARACYCLOPHANE-1;5-DIENE);POLY(VINYLFERROCENE);ELECTROCHEMISTRY;ROUTE