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Organometallic Gels: Characterization and Electrochemical Studies of Swellable, Thermally Crosslinked Poly(ferrocenylsilane)s
Author(s) -
Kulbaba Kevin,
MacLachlan Mark J.,
Evans Christopher E. B.,
Manners Ian
Publication year - 2001
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/1521-3935(20010601)202:9<1768::aid-macp1768>3.0.co;2-t
Subject(s) - swelling , polymer chemistry , copolymer , dichloromethane , chloroform , electrochemistry , solvent , thermal stability , chemistry , hildebrand solubility parameter , materials science , polymer , electrode , organic chemistry , composite material
Investigations on a series of crosslinked poly(ferrocenylsilane) networks that have been prepared via the ring‐opening copolymerization of the silicon‐bridged [1]ferrocenophane fcSiMe 2 (fc = Fe( η ‐C 5 H 4 ) 2 ) with controlled amounts of a spirocyclic [1]ferrocenophane fcSi(CH 2 ) 3 are reported. These crosslinked poly(ferrocenylsilane)s have improved thermal stability relative to their linear counterparts. The swelling response was investigated as a function of temperature, solvent and crosslink density. As expected, the degree of crosslinking had a dramatic effect on the swelling in various media. From swelling measurements in a variety of liquids, it was determined that the best solvents for poly(ferrocenyldimethylsilane) are THF, chloroform, and dichloromethane. The solubility parameter ( δ ) for the linear homopolymer was found to be 18.7(7) MPa 1/2 . Reversible electrochemical oxidation of the gel was observed at oxidation potentials greater than 450 mV (vs Ag/AgCl), consistent with the oxidation potential of the linear homopolymer, and an intervalence charge transfer band was detected at 1300 nm for the partially oxidized material.