Polyferrocenylsilane homopolymers and diblock copolymers with pendant ruthenocenyl groups by photocontrolled ring-opening polymerisation

Maximilian Erhard, Kevin Lam, Mairi Haddow, George R. Whittell, William E. Geiger, Ian Manners

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The strained, sila[1]ferrocenophane [{Fe(η-C5H 4)2}SiMe(η-C5H4)Ru(η-C 5H5)] (4) has been prepared by the reaction of Li[(η-C5H4)Ru(η-C5H5)] (8) with [{Fe(η-C5H4)2}SiMeCl] (7). Two different routes for the synthesis of 8 were investigated, which differed predominately in the purity of the product obtained. Although the thermal ring-opening polymerisation (ROP) of 4 failed to yield soluble polymeric material, photocontrolled ROP using Na[C5H5] as the initiator afforded relatively monodisperse, soluble polymers of predetermined molecular weights and the general formula [(η-C5H 4)Fe(η-C5H4)SiMe{(η-C5H 4)Ru(η-C5H5)}]n (19). This material was stable to both oxygen and moisture. Electrochemical characterisation of 4 revealed unusual, concentration dependent behaviour as a consequence of the oxidation of the ruthenocenyl groups. This phenomenon was not observed upon oxidation of the Ru centres in 19, presumably due to the sterically encumbered structure of the polymer. The photocontrolled ROP protocol was extended to afford the block copolymers polystyrene (PS) n-b-[(η-C5H4)Fe(η-C5H 4)SiMe{(η-C5H4)Ru(η-C5H 5)}]m (22) by the application of a PS-based macroinitiator. These materials represent rare examples of complex polymer architectures where two different metals are incorporated in the same block.

Original languageEnglish
Pages (from-to)1264-1274
Number of pages11
JournalPolymer Chemistry
Volume5
Issue number4
DOIs
Publication statusPublished - Feb 21 2014

ASJC Scopus subject areas

  • Bioengineering
  • Biochemistry
  • Polymers and Plastics
  • Organic Chemistry

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