Organometallic Polymers Based on S-S and Se-Se Linked n-Butylferrocenes

David L. Compton, Paul F. Brandt, Thomas B. Rauchfuss, Darren F. Rosenbaum, Charles F. Zukoski

Research output: Contribution to journalArticlepeer-review

Abstract

Polyferrocenylene persulfides, [(BuC5H3)(C5H4)FeS2] n, have been prepared by desulfurization of butyltrithiaferrocenophane (BuC5H3)(C5H4)FeS3. The molecular precursor was prepared by dilithiation of butylferrocene followed by treatment with elemental sulfur and isolated as a 7:1 mixture of the 1,3,1′ and 1,2,1′ isomers. The trisulfide was converted to polymer by treatment with the desulfurization agent PBu3. The rate of this desulfurization and the nature of the polymer depends critically on the reaction solvent. Desulfurization in DMF and THF afforded insoluble but swellable rubbers. Desulfurization of BufcS3 in mixed CH2Cl2-THF solutions gave soluble polymers with Mn ranging from 12 000 to 359 000, with lower molecular weight products being favored at high [CH2Cl2]. The effect of high [CH2Cl2] was modeled by the reaction of [fcS2]n with a CH2Cl2 solution of PBu3 to give fcS2CH2. Molecular weights for [BufcS2]n were confirmed by light scattering measurements. Soluble [BufcS2]n undergoes reversible electrochemical oxidation in two steps, centered at 780 V (vs Ag/AgCl) and separated by ∼300 mV. The first oxidation potential is similar to that for the trisulfide monomer and is thought to correspond to oxidation of alternating Fe centers, followed by conversion of the remaining FeII sites. The polymers photodegrade upon exposure to UV light in air. Deselenization of BufcSe3 gave red soluble [BufcSe2]n with only moderate molecular weights and with high polydispersities. The microstructure of this polymer was established by 77Se NMR studies which support the presence of head-to-head, head-to-tail, and tail-to-tail dyads.

Original languageEnglish (US)
Pages (from-to)2342-2349
Number of pages8
JournalChemistry of Materials
Volume7
Issue number12
DOIs
StatePublished - Dec 1995

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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